TW201333075A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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Abstract
Description
本發明係關於液晶配向劑(亦稱為液晶配向處理劑)、由該液晶配向劑所得之液晶配向膜、及具有該液晶配向膜之液晶顯示元件。 The present invention relates to a liquid crystal alignment agent (also referred to as a liquid crystal alignment treatment agent), a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
液晶配向膜對於使用液晶顯示元件或聚合性液晶的位相差板等,其為欲將液晶分子的配向方向控制為一定之膜。液晶配向膜對於液晶顯示元件等而言,與液晶等同時皆為非常重要之構成構件。 The liquid crystal alignment film is a phase difference plate or the like using a liquid crystal display element or a polymerizable liquid crystal, and is a film for controlling the alignment direction of liquid crystal molecules to be constant. The liquid crystal alignment film is a very important constituent member for liquid crystal display elements and the like at the same time as liquid crystal.
近年來,對於日益進步的液晶顯示元件之領域,液晶配向膜除被要求具有控制液晶之配向的性能(以下亦稱為液晶配向性),亦被要求耐熱性或耐溶劑性等。且,欲使液晶顯示元件發揮高性能,亦要求其他多樣特性。 In recent years, in the field of increasingly advanced liquid crystal display elements, the liquid crystal alignment film is required to have a property of controlling the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment), and is also required to have heat resistance or solvent resistance. Further, in order to make the liquid crystal display element exhibit high performance, various other characteristics are also required.
作為液晶配向膜上所求的特性之1,其為有關提高液晶顯示元件之顯示品位的特性。例如對於液晶顯示元件,被要求顯示不良之改善,作為顯示不良對策,被要求液晶配向膜的特性提高。 As a characteristic obtained on the liquid crystal alignment film, it is a characteristic for improving the display quality of the liquid crystal display element. For example, in the liquid crystal display device, improvement in display failure is required, and as a countermeasure against display failure, the characteristics of the liquid crystal alignment film are required to be improved.
特別為在最近急速高精細化的行動電話或平板型之端末中,對於所使用的液晶顯示元件亦被要求高顯示品位。其結果,對於所謂「殘像現象」或者僅稱為「殘像」之顯示不良的規格亦日益嚴苛。例如即使產生殘像,期待具有必需快速使其消失之特性的液晶配向膜的實現。對於近年 之液晶顯示元件,因使用環境並未限制於室內,故期待屋外.車內高溫場所亦具有高品質性能,求得殘像特性在室溫與高溫下亦不會產生變化之液晶配向膜。 In particular, in the end of the recent rapid and high-definition mobile phone or tablet type, a high display quality is required for the liquid crystal display element to be used. As a result, the specifications for the display failure of the so-called "after-image phenomenon" or simply "after-image" are becoming more and more severe. For example, even if an afterimage is generated, realization of a liquid crystal alignment film having characteristics that it is necessary to quickly disappear is expected. For recent years The liquid crystal display element is not restricted to indoors due to the use environment, so it is expected to be outside. The high temperature environment in the car also has high quality performance, and the liquid crystal alignment film which does not change at room temperature and high temperature is obtained.
又,對於行動電話等行動端末,期待液晶顯示元件之低消費電力化。對於如此可攜帶的端末,因液晶顯示元件的低消費電力化,可實現1次電池充電下可長期間之使用。對於液晶顯示元件之低消費電力化,液晶顯示元件的高透過率化為有效。因此,在液晶顯示元件中,對於畫素高開口率等之同時對於液晶配向膜等構成構件,亦期待透過率之提高。 Moreover, it is expected that the liquid crystal display element will be low in power consumption at the end of the mobile terminal. For such a portable terminal, since the liquid crystal display element is low in power consumption, it can be used for a long period of time under battery charging. For the low power consumption of the liquid crystal display element, the high transmittance of the liquid crystal display element is effective. Therefore, in the liquid crystal display device, it is expected that the transmittance is improved for a constituent member such as a liquid crystal alignment film at the same time as a high aperture ratio of the pixel.
且,液晶配向膜由對於液晶顯示元件之製造步驟的適用性觀點來看,期待對於磨擦處理之高耐性。對於磨擦處理已知有在液晶顯示元件之製造步驟上,形成液晶配向膜之方法,現在亦廣泛使用於工業上。對於磨擦處理,於基板上形成聚醯亞胺等高分子膜,將其表面以布擦拭進行配向處理。 Further, the liquid crystal alignment film is expected to have high resistance to the rubbing treatment from the viewpoint of applicability to the manufacturing steps of the liquid crystal display element. A method of forming a liquid crystal alignment film in the manufacturing steps of a liquid crystal display element is known for the rubbing treatment, and is now widely used in the industry. For the rubbing treatment, a polymer film such as polyimide or a polyimide film is formed on the substrate, and the surface thereof is wiped with a cloth to perform an alignment treatment.
對於磨擦處理,有著液晶配向膜在切削時所產生的粉塵或附在液晶配向膜的傷痕,而使顯示品位降低的問題。因此,期待液晶配向膜對於磨擦處理之耐性(以下亦稱為耐擦性)。 In the rubbing treatment, there is a problem that the liquid crystal alignment film is generated by dust generated during cutting or a flaw attached to the liquid crystal alignment film to lower the display quality. Therefore, the resistance of the liquid crystal alignment film to the rubbing treatment (hereinafter also referred to as rubbing resistance) is expected.
作為欲形成具有高耐擦性之液晶配向膜的方法,已知有於構成液晶配向膜之聚醯亞胺、或欲形成其聚醯亞胺之聚醯亞胺前驅物中添加種種添加劑的方法(例如參照專利文獻1、2)。 As a method for forming a liquid crystal alignment film having high rub resistance, a method of adding various additives to a polyimine comprising a liquid crystal alignment film or a polyimine precursor to form a polyimine is known. (For example, refer to Patent Documents 1 and 2).
其他亦有提出耐擦性良好之聚醯亞胺結構等(例如參照專利文獻3、4)。 Others have proposed a polyimine structure or the like having good rubbing resistance (for example, refer to Patent Documents 3 and 4).
藉由如此方法,可使磨擦處理時之液晶配向膜磨削(亦稱為磨擦削)或液晶配向膜的傷痕(亦稱為磨擦傷)難以產生。 By such a method, it is possible to make the liquid crystal alignment film grinding (also referred to as abrasion) or the liquid crystal alignment film scratch (also referred to as abrasion) in the rubbing treatment difficult to produce.
然而,近年來,在液晶顯示元件的一部份用途上,對於磨擦處理,有著將聚醯亞胺等高分子膜以布用力擦拭而進行配向處理之傾向。如此強磨擦處理,係以使液晶配向狀態成為更均勻,且更強固者作為目的。因此,對於液晶配向膜,要求更高水準的耐擦性。 However, in recent years, in some applications of liquid crystal display elements, in the rubbing treatment, a polymer film such as polyimine has a tendency to be wiped by a cloth and subjected to alignment treatment. Such a strong rubbing treatment is intended to make the liquid crystal alignment state more uniform and stronger. Therefore, for the liquid crystal alignment film, a higher level of rub resistance is required.
〔專利文獻1〕日本特開平7-120769號公報 [Patent Document 1] Japanese Patent Laid-Open No. 7-120769
〔專利文獻2〕日本特開平9-146100號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 9-146100
〔專利文獻3〕日本特開2008-90297號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-90297
〔專利文獻4〕日本特開平9-258229號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei 9-258229
本發明的目的係為提供一種具有高液晶配向性與耐擦性,對於液晶顯示元件在廣泛溫度範圍下具有殘像減低效果,且可形成高光透過率的液晶配向膜之液晶配向劑。 An object of the present invention is to provide a liquid crystal alignment agent which has a high liquid crystal alignment property and abrasion resistance, and which has an afterimage reduction effect on a liquid crystal display element over a wide temperature range and which can form a high light transmittance.
又,本發明的目的為提供一種使用如上述之液晶配向劑,具有高液晶配向性與耐擦性,對於液晶顯示元件在廣 泛溫度範圍的殘像減低上為有效,且高光透過率之液晶配向膜。且,提供具有該液晶配向膜之液晶顯示元件。 Further, an object of the present invention is to provide a liquid crystal alignment agent as described above, which has high liquid crystal alignment and rub resistance, and is widely used for liquid crystal display elements. The afterimage in the over-temperature range is reduced in the liquid crystal alignment film which is effective and has high light transmittance. Further, a liquid crystal display element having the liquid crystal alignment film is provided.
本發明者們,欲解決上述課題進行重複詳細檢討結果後完成本發明。 The inventors of the present invention have completed the present invention by repeating the detailed review results to solve the above problems.
即,本發明為具有以下要旨者。 That is, the present invention has the following gist.
(1)一種液晶配向劑,其為含有將二胺成分與四羧酸衍生物進行反應後所得之聚醯亞胺前驅物的液晶配向劑,其特徵為二胺成分為含有20莫耳%以上100莫耳%以下的含有量之下述式(1)所示二胺化合物,且四羧酸衍生物為含有50莫耳%以上未達100莫耳%的含有量之芳香族四羧基衍生物、或二胺成分為含有20莫耳%以上未達100莫耳%之含有量的下述式(1)所示二胺化合物,且四羧酸衍生物為含有50莫耳%以上100莫耳%以下的含有量之芳香族四羧酸衍生物。 (1) A liquid crystal alignment agent which is a liquid crystal alignment agent containing a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid derivative, and is characterized in that the diamine component contains 20 mol% or more. a diamine compound represented by the following formula (1) in an amount of 100 mol% or less, and the tetracarboxylic acid derivative is an aromatic tetracarboxylic derivative containing 50 mol% or more and less than 100 mol% Or the diamine component is a diamine compound represented by the following formula (1) containing 20 mol% or more and less than 100 mol%, and the tetracarboxylic acid derivative contains 50 mol% or more and 100 mol%. An aromatic tetracarboxylic acid derivative having a content of less than %.
(2)前述二胺成分進一步含有下述式(AM1)所示 二胺化合物之上述(1)所記載的液晶配向劑。 (2) The diamine component further contains the following formula (AM1) A liquid crystal alignment agent according to (1) above, which is a diamine compound.
(3)上述式(AM1)所示二胺化合物中,R5為具有選自上述式(a-1)、式(a-4)、式(a-5)、式(a-6)、式(a-10)、式(a-16)、式(a-19)及式(a-20)所成群的1種結構的二胺化合物之上述(2)所記載的液晶配向劑。 (3) In the diamine compound represented by the above formula (AM1), R 5 is selected from the group consisting of the above formula (a-1), formula (a-4), formula (a-5), and formula (a-6). A liquid crystal alignment agent according to the above (2), which is a diamine compound having a single structure of the formula (a-10), the formula (a-16), the formula (a-19), and the formula (a-20).
(4)前述二胺成分含有50莫耳%以上未達100莫耳%之含有量的上述式(1)所示二胺化合物的上述(1)~(3)中任一所記載的液晶配向劑。 (4) The liquid crystal alignment according to any one of the above (1) to (3), wherein the diamine component contains 50 mol% or more and less than 100 mol% of the diamine compound of the formula (1). Agent.
(5)前述四羧酸衍生物為選自下述式(2-a)~式(2-e)所示化合物所成群的1種以上化合物的上述(1)~(4)中任一所記載的液晶配向劑。 (5) The tetracarboxylic acid derivative is any one of the above (1) to (4) selected from the group consisting of a compound represented by the following formula (2-a) to the formula (2-e); The liquid crystal alignment agent described.
(6)前述四羧酸衍生物為上述式(2-a)之上述(5)所記載的液晶配向劑。 (6) The tetracarboxylic acid derivative is the liquid crystal alignment agent of the above (5) of the above formula (2-a).
(7)由上述(1)~(6)中任一所記載的液晶配向劑所得之液晶配向膜。 (7) A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of the above (1) to (6).
(8)具有上述(7)所記載的液晶配向膜為特徵之液晶顯示元件。 (8) A liquid crystal display element characterized by comprising the liquid crystal alignment film according to (7) above.
本發明可提供具有高液晶配向性與耐擦性,對於液晶顯示元件之殘像減低為有效,且可形成高光透過率之液晶配向膜的液晶配向劑。 The present invention can provide a liquid crystal alignment agent which has high liquid crystal alignment and rub resistance, is effective for reducing the afterimage of a liquid crystal display element, and can form a liquid crystal alignment film having high light transmittance.
又,本發明可提供使用上述液晶配向劑,具有高液晶配向性與耐擦性,對於液晶顯示元件之殘像減低為有效,且高光透過率之液晶配向膜。 Further, the present invention can provide a liquid crystal alignment film which has high liquid crystal alignment property and abrasion resistance and which is effective for reducing the afterimage of a liquid crystal display element and has high light transmittance.
且本發明可提供使用具有如上述特性之液晶配向膜的液晶顯示元件。 Further, the present invention can provide a liquid crystal display element using a liquid crystal alignment film having the above characteristics.
本發明的液晶配向劑含有將二胺成分與四羧酸衍生物進行反應所得之聚醯亞胺前驅物。作為聚醯亞胺前驅物,含有聚醯胺酸、聚醯胺酸酯等。 The liquid crystal alignment agent of the present invention contains a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid derivative. As a polyimide precursor, it contains poly-proline, polyphthalate, and the like.
本發明的液晶配向劑所含之聚醯亞胺前驅物為,藉由具有特徵結構之二胺成分與該二胺成分之組合,使用在所望特性之實現上較佳的四羧酸衍生物而形成。 The polyimine precursor contained in the liquid crystal alignment agent of the present invention is a tetracarboxylic acid derivative which is preferably realized by a desired property by a combination of a diamine component having a characteristic structure and the diamine component. form.
以下對於欲得到本發明液晶配向劑所含有之聚醯亞胺前驅物時所使用的二胺成分及四羧酸衍生物等做詳細說明。 Hereinafter, the diamine component and the tetracarboxylic acid derivative used in order to obtain the polyimine precursor contained in the liquid crystal alignment agent of the present invention will be described in detail.
本發明的液晶配向劑為,作為欲得到所含有之聚醯胺酸、聚醯胺酸酯等聚醯亞胺前驅物的二胺成分,使用下述式(1)所示特定結構之特定二胺化合物。 The liquid crystal alignment agent of the present invention is a specific component of the specific structure represented by the following formula (1), which is a diamine component of a polyimine precursor such as polyglycolic acid or polyglycolate to be contained. Amine compound.
上述式(1)中,X為氧原子或硫原子,Y1及Y2獨立為單鍵、-O-、-S-、-OCO-、或COO-,R1及R2獨立為碳數1~3的伸烷基。 In the above formula (1), X is an oxygen atom or a sulfur atom, and Y 1 and Y 2 are independently a single bond, -O-, -S-, -OCO-, or COO-, and R 1 and R 2 are independently a carbon number. 1 to 3 alkyl groups.
上述式(1)中之X為氧原子時,上述式(1)的特定二胺化合物為具有脲基之二胺化合物,X為硫原子時,其為具有硫脲基(以下有時將脲基及硫脲基總稱為(硫)脲基)的二胺化合物。 When X in the above formula (1) is an oxygen atom, the specific diamine compound of the above formula (1) is a diamine compound having a urea group, and when X is a sulfur atom, it has a thiourea group (hereinafter sometimes urea) The base and the thiourea group are collectively referred to as (thio)ureido) diamine compounds.
作為前述式(1)所示二胺化合物之較佳例子,可舉出下述式之化合物。其中,式(1-1)、式(1-5)~式(1-8)所示化合物為佳。 Preferable examples of the diamine compound represented by the above formula (1) include compounds of the following formula. Among them, the compound represented by the formula (1-1) and the formula (1-5) to the formula (1-8) is preferred.
欲得到本發明之液晶配向劑所含有的聚醯亞胺前驅物之二胺成分,雖含有上述式(1)特定二胺化合物作為必須成分,但作為所含有之特定二胺化合物的含有量可為任意值。 The diamine component of the polyimine precursor which is contained in the liquid crystal alignment agent of the present invention contains the specific diamine compound of the above formula (1) as an essential component, but the content of the specific diamine compound contained therein may be Is any value.
由本發明的液晶配向劑所得之液晶配向膜,欲得到充分的耐擦性,全二胺成分(100莫耳%)中,上述式(1)之特定二胺化合物以20莫耳%以上為佳,較佳為30莫耳%以上,更佳為50莫耳%以上。 In the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention, in order to obtain sufficient rub resistance, in the total diamine component (100 mol%), the specific diamine compound of the above formula (1) is preferably 20 mol% or more. Preferably, it is 30 mol% or more, more preferably 50 mol% or more.
又,由液晶配向劑所含之聚醯亞胺前驅物形成聚醯亞胺,作為液晶配向膜使用液晶顯示元件時的液晶的預傾角之最適化、或由減低蓄積電荷等觀點來看,上述式(1)所示特定二胺化合物之含有量在全二胺成分中以未達100莫耳%者為佳,較佳為30~60%。 In addition, the polyimine precursor contained in the liquid crystal alignment agent forms a polyimine, and the liquid crystal display element is optimized as a liquid crystal display element, and the pretilt angle of the liquid crystal is optimized, or the charge is reduced. The content of the specific diamine compound represented by the formula (1) is preferably less than 100 mol%, preferably 30 to 60%, based on the total diamine component.
上述式(1)所示特定二胺化合物的含有量在全二胺成分中為100莫耳%時,即二胺成分皆為上述式(1)所示特定二胺化合物時,如後述,使用於聚醯亞胺前驅物之形成上的四羧酸衍生物中的芳香族四羧酸衍生物之含有量為全四羧酸成分中,50莫耳%以上未達100莫耳%。因此,本發明的液晶配向劑中,二胺成分皆為上述式(1)之特定二胺化合物的同時,四羧酸衍生物不會皆為芳香族四羧 酸衍生物。 When the content of the specific diamine compound represented by the above formula (1) is 100 mol% in the total diamine component, that is, when the diamine component is a specific diamine compound represented by the above formula (1), it is used as described later. The content of the aromatic tetracarboxylic acid derivative in the tetracarboxylic acid derivative in the formation of the polyimine precursor is 50 mol% or more and less than 100 mol% in the all tetracarboxylic acid component. Therefore, in the liquid crystal alignment agent of the present invention, the diamine component is a specific diamine compound of the above formula (1), and the tetracarboxylic acid derivative is not all aromatic tetracarboxylic acid. Acid derivative.
於本發明之液晶配向劑所含之聚醯亞胺前驅物,係由含有上述式(1)所示特定二胺化合物作為必須成分之二胺成分、與四羧酸衍生物之反應而得。 The polyimine precursor contained in the liquid crystal alignment agent of the present invention is obtained by a reaction of a diamine component containing a specific diamine compound represented by the above formula (1) as an essential component and a tetracarboxylic acid derivative.
又,欲得到本發明之聚醯亞胺前驅物的二胺成分時,與上述式(1)所示特定二胺化合物之同時,併用下述式(AM1)所示二胺化合物,使用於與四羧酸衍生物之反應上者為佳。 Further, when the diamine component of the polyimine precursor of the present invention is obtained, the diamine compound represented by the following formula (AM1) is used together with the specific diamine compound represented by the above formula (1). The reaction of the tetracarboxylic acid derivative is preferred.
上述式(AM1)中,R5表示具有選自下述式(a-1)~式(a-19)所成群的1種結構的2價有機基,R3及R4獨立表示氫原子或1價有機基。 In the above formula (AM1), R 5 represents a divalent organic group having one structure selected from the group consisting of the following formulas (a-1) to (a-19), and R 3 and R 4 independently represent a hydrogen atom. Or a monovalent organic group.
上述式(AM1)所示二胺化合物為,由液晶配向劑所含之聚醯亞胺前驅物形成聚醯亞胺後,由作為液晶配向膜適用於液晶顯示元件時的殘像減低等觀點來看,R5為具有選自上述式(a-1)、式(a-4)、式(a-5)、式(a-6)、式(a-10)、式(a-16)、式(a-19)及式(a-20)所成群的1種結構之二胺化合物為較佳。特佳為具有選自(a-1)、(A-4)、(A-19)及(a-20)所成群的1種結構之二胺化合物。 The diamine compound represented by the above formula (AM1) is obtained by forming a polyimine from a polyimide precursor contained in a liquid crystal alignment agent, and reducing the afterimage when the liquid crystal alignment film is used as a liquid crystal display element. It is to be noted that R 5 has a formula (a-1), a formula (a-4), a formula (a-5), a formula (a-6), a formula (a-10), and a formula (a-16). A diamine compound having one structure in the group of the formula (a-19) and the formula (a-20) is preferred. Particularly preferred is a diamine compound having one structure selected from the group consisting of (a-1), (A-4), (A-19) and (a-20).
又,欲得到本發明之液晶配向劑所含有之聚醯亞胺前驅物的二胺成分,將上述式(1)特定二胺化合物作為必須成分,可含有上述式(AM1)所示二胺化合物,但亦可含有此以外之二胺化合物。 In addition, the diamine component of the polyimine precursor which is contained in the liquid crystal alignment agent of the present invention may contain the diamine compound represented by the above formula (AM1) as an essential component of the specific diamine compound of the above formula (1). However, it is also possible to contain a diamine compound other than this.
即,欲得到本發明的液晶配向劑所含有之聚醯亞胺前驅物的二胺成分,以不損害本發明的效果之範圍下,可含有上述式(1)之特定二胺化合物及上述式(AM1)的二胺化合物以外之二胺化合物。 In other words, the diamine component of the polyimine precursor which is contained in the liquid crystal alignment agent of the present invention may contain the specific diamine compound of the above formula (1) and the above formula without departing from the effects of the present invention. A diamine compound other than the diamine compound of (AM1).
欲得到本發明的液晶配向劑所含有之聚醯亞胺前驅物時可使用的四羧酸衍生物並無特別限定。 The tetracarboxylic acid derivative which can be used in order to obtain the polyimine precursor contained in the liquid crystal alignment agent of the present invention is not particularly limited.
作為本發明之四羧酸衍生物,可舉出四羧酸二酐(下述式(2-a)所示)、四羧酸一酐(下述式(2-b)所示)、四羧酸(下述式(2-d)所示)、二羧酸二烷基酯(下述式(2-c)所示)、二羧酸氯化物二烷基酯(下述式(2-e)所示)等。作為四羧酸衍生物,僅為可與二胺進行反應者即可,並無限定於此等。 Examples of the tetracarboxylic acid derivative of the present invention include tetracarboxylic dianhydride (shown by the following formula (2-a)), tetracarboxylic acid monoanhydride (shown by the following formula (2-b)), and four. a carboxylic acid (shown by the following formula (2-d)), a dialkyl dicarboxylate (shown by the following formula (2-c)), a dicarboxylic acid chloride dialkyl ester (the following formula (2) -e) shown) and so on. The tetracarboxylic acid derivative is only required to be reacted with a diamine, and is not limited thereto.
適用於本發明之四羧酸衍生物為可選自下述式(2-a)~式(2-e)所示化合物所成群的1種以上化合物。 The tetracarboxylic acid derivative to be used in the present invention is one or more compounds selected from the group consisting of the compounds represented by the following formulas (2-a) to (2-e).
其中,R7表示烷基。 Wherein R 7 represents an alkyl group.
又,作為R6的具體例,可舉出以下之式〔A-1〕~式〔A-47〕。 Further, specific examples of R 6 include the following formula [A-1] to formula [A-47].
作為欲得到本發明的液晶配向劑所含之聚醯亞胺前驅物時可使用的四羧酸衍生物,特別以芳香族四羧酸衍生物的使用為佳。所有四羧酸衍生物可為芳香族四羧酸衍生物。 The tetracarboxylic acid derivative which can be used in order to obtain the polyimine precursor contained in the liquid crystal alignment agent of the present invention is particularly preferably used as an aromatic tetracarboxylic acid derivative. All tetracarboxylic acid derivatives may be aromatic tetracarboxylic acid derivatives.
欲得到上述聚醯亞胺前驅物,可使用2種以上四羧酸衍生物,可使用於與二胺成分之反應上。對於此情況下,於四羧酸衍生物中含有1種以上的芳香族四羧酸衍生物者為佳。 In order to obtain the above polyimine precursor, two or more kinds of tetracarboxylic acid derivatives can be used, and it can be used for the reaction with a diamine component. In this case, it is preferred that one or more aromatic tetracarboxylic acid derivatives are contained in the tetracarboxylic acid derivative.
又,所有四羧酸衍生物為芳香族四羧酸衍生物時,可使用2種以上的結構相異的芳香族四羧酸衍生物者。 Further, when all the tetracarboxylic acid derivatives are aromatic tetracarboxylic acid derivatives, two or more kinds of aromatic tetracarboxylic acid derivatives having different structures may be used.
作為四羧酸衍生物,藉由含有芳香族四羧酸衍生物,可使用於聚醯亞胺前驅物的形成上,可提高所得之液晶配向膜的液晶配向性。此時,對於所使用的四羧酸衍生物全量,芳香族四羧酸衍生物之含有量以50莫耳%以上為較佳。但,使用於聚醯亞胺前驅物之形成的二胺成分皆為上述式(1)所示二胺化合物時,如上述,芳香族四羧酸衍生物的含有量對於使用的四羧酸衍生物全量而言為未達100莫耳%。 By containing an aromatic tetracarboxylic acid derivative, the tetracarboxylic acid derivative can be used for the formation of a polyimide precursor, and the liquid crystal alignment property of the obtained liquid crystal alignment film can be improved. In this case, the total amount of the tetracarboxylic acid derivative to be used is preferably 50 mol% or more of the aromatic tetracarboxylic acid derivative. However, when the diamine component used for the formation of the polyimide precursor is the diamine compound represented by the above formula (1), as described above, the content of the aromatic tetracarboxylic acid derivative is derived from the tetracarboxylic acid used. The total amount is less than 100% by mole.
作為欲得到本發明的液晶配向劑所含之聚醯亞胺前驅物所使用的較佳芳香族四羧酸衍生物,可舉出選自上述式(2-a)~式(2-e)所示化合物所成群的1種以上化合物,R7表示烷基,R6表示具有選自下述式(b-1)~式(b-8)所成群的1種結構的4價有機基、芳香族四羧酸衍生物。 The preferred aromatic tetracarboxylic acid derivative to be used for obtaining the polyimine precursor contained in the liquid crystal alignment agent of the present invention is selected from the above formula (2-a) to formula (2-e). In the compound of the above-mentioned compound, R 7 represents an alkyl group, and R 6 represents a tetravalent organic compound having one structure selected from the group consisting of the following formulas (b-1) to (b-8). A base, an aromatic tetracarboxylic acid derivative.
上述式(2-a)~式(2-e)所示,R6為上述式(b-1)所示結構的芳香族四羧酸衍生物中,上述R6的具體例相當於上述式〔A-26〕之四羧酸衍生物。 The above-described formula (2-a) ~ the formula (2-e) as shown, R 6 above formula (b-1) an aromatic tetracarboxylic acid derivative structure shown in the above-described specific examples of R 6 corresponds to the formula a tetracarboxylic acid derivative of [A-26].
同樣地,R6為上述式(b-2)所示結構的芳香族四羧酸衍生物中,R6的具體例相當於上述式〔A-27〕之四羧酸衍生物。 Likewise, R 6 is a configuration of an aromatic tetracarboxylic acid derivative (b-2) shown in the above formula, specific examples of R 6 corresponds to the formula [A-27] The tetracarboxylic acid derivative.
R6為上述式(b-3)所示結構的芳香族四羧酸衍生物中,R6的具體例相當於上述式〔A-28〕之四羧酸衍生物。 R 6 is an aromatic tetracarboxylic acid derivative represented by the above structure formula (b-3), a specific R 6 corresponds to the above embodiment of formula [A-28] The tetracarboxylic acid derivative.
R6為上述式(b-4)所示結構的芳香族四羧酸衍生物 中,R6的具體例相當於上述式〔A-29〕之四羧酸衍生物。 R 6 is an aromatic tetracarboxylic acid derivative represented by the above structural formula (b-4), the specific examples of R 6 corresponds to the formula [A-29] The tetracarboxylic acid derivative.
R6為上述式(b-5)所示結構的芳香族四羧酸衍生物中,R6的具體例相當於上述式〔A-31〕之四羧酸衍生物。 R 6 above formula [A-31] of the above-described tetracarboxylic acid derivative of formula (b-5) an aromatic tetracarboxylic acid derivative structure shown in specific examples of R 6 corresponds.
R6為上述式(b-6)所示結構的芳香族四羧酸衍生物中,R6的具體例相當於上述式〔A-30〕之四羧酸衍生物。 R 6 is an aromatic tetracarboxylic acid derivative represented by the above structural formula (b-6), a specific R 6 corresponds to the above embodiment of formula [A-30] The tetracarboxylic acid derivative.
R6為上述式(b-7)所示結構的芳香族四羧酸衍生物中,R6的具體例相當於上述式〔A-32〕之四羧酸衍生物。 R 6 is an aromatic tetracarboxylic acid derivative represented by the above structural formula (b-7), the specific examples of R 6 corresponds to the formula [A-32] The tetracarboxylic acid derivative.
R6為上述式(b-8)所示結構的芳香族四羧酸衍生物中,R6的具體例相當於上述式〔A-47〕之四羧酸衍生物。 R 6 is an aromatic tetracarboxylic acid derivative represented by the above structure formula (b-8), a specific R 6 corresponds to the above embodiment of formula [A-47] The tetracarboxylic acid derivative.
作為欲得到本發明的液晶配向劑所含之聚醯亞胺前驅物所使用的特佳芳香族四羧酸衍生物,可舉出選自上述式(2-a)~式(2-e)所示化合物所成群的1種以上化合物,R7為烷基,R6為上述式(b-1)、式(b-2)、式(b-7)所示結構的芳香族四羧酸衍生物。 The particularly preferred aromatic tetracarboxylic acid derivative used for obtaining the polyimine precursor contained in the liquid crystal alignment agent of the present invention is selected from the above formula (2-a) to formula (2-e). One or more compounds in which the compounds are grouped, R 7 is an alkyl group, and R 6 is an aromatic tetracarboxylic acid having a structure represented by the above formula (b-1), formula (b-2) or formula (b-7). Acid derivative.
作為欲得到本發明的液晶配向劑所含之聚醯亞胺前驅物的方法,可利用公知方法。 As a method of obtaining the polyimine precursor contained in the liquid crystal alignment agent of the present invention, a known method can be used.
含有上述上述式(1)之特定二胺化合物作為必須成分之二胺成分、與含有芳香族四羧酸衍生物之四羧酸衍生物進行反應後得到聚醯亞胺前驅物。 The diamine component containing the specific diamine compound of the above formula (1) as an essential component and a tetracarboxylic acid derivative containing an aromatic tetracarboxylic acid derivative are reacted to obtain a polyimide precursor.
作為四羧酸衍生物,使用四羧酸二酐時的例子如以下說明。 An example of using a tetracarboxylic dianhydride as a tetracarboxylic acid derivative is as follows.
使用於本發明的液晶配向劑所含有之聚醯亞胺前驅物 的製造之二胺成分與四羧酸衍生物的聚合反應方法並無特別限定。在有機溶劑中可使彼等混合後進行聚合反應,成為聚醯亞胺前驅物之聚醯胺酸。又,將聚醯胺酸使用公知酯化劑使羧酸基進行酯化時,可得到聚醯胺酸酯。聚醯亞胺係可由將所得之聚醯胺酸及聚醯胺酸酯進行脫水閉環而得。 Polyimine precursor used in the liquid crystal alignment agent of the present invention The polymerization reaction method of the produced diamine component and the tetracarboxylic acid derivative is not specifically limited. In an organic solvent, they may be mixed and then subjected to a polymerization reaction to form a poly-proline which is a polyimide precursor. Further, when the polyamic acid is esterified with a known esterifying agent to obtain a carboxylic acid group, a polyphthalate can be obtained. The polyimine can be obtained by subjecting the obtained polylysine and polyphthalate to dehydration ring closure.
作為將二胺成分與四羧酸衍生物在有機溶劑中混合之方法,可舉出將二胺成分於有機溶劑中分散或者溶解之溶液進行攪拌,直接添加四羧酸衍生物成分之方法、或將四羧酸衍生物成分於有機溶劑中分散或者溶解後添加之方法。 A method of mixing a diamine component and a tetracarboxylic acid derivative in an organic solvent, a method of stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and directly adding a tetracarboxylic acid derivative component, or A method in which a tetracarboxylic acid derivative component is dispersed or dissolved in an organic solvent and then added.
且將四羧酸衍生物於有機溶劑分散或者溶解的溶液中添加二胺成分之方法、或將四羧酸衍生物與二胺交互添加之方法等可舉出。又,四羧酸衍生物成分及二胺中至少一方係由複數種化合物所成時,這些複數種成分可預先混合之狀態下進行聚合反應,或各別順序下進行聚合反應。 Further, a method of adding a diamine component to a solution in which a tetracarboxylic acid derivative is dispersed or dissolved in an organic solvent, or a method of mutually adding a tetracarboxylic acid derivative and a diamine may be mentioned. Further, when at least one of the tetracarboxylic acid derivative component and the diamine is formed of a plurality of compounds, the plurality of components may be subjected to a polymerization reaction in a state of being mixed in advance, or a polymerization reaction may be carried out in a separate order.
將二胺成分與四羧酸衍生物在有機溶劑中進行聚合反應時的溫度一般為0~150℃,以5~100℃為佳,較佳為10~80℃。溫度較高者聚合反應較早結束,但若過高時無法得到高分子量的聚合物。又,聚合反應可在任意裝入濃度下進行,但若裝入濃度過低時,得到高分子量的聚合物變的困難,裝入濃度過高時,反應液的黏性會過高而均勻的攪拌變的困難,故以1~50質量%為佳,較佳為5~30質量%。聚合反應初期在高濃度下進行,其後可追加有機溶 劑。且上述的裝入濃度係為合併二胺成分與四羧酸衍生物之合計質量的濃度。 The temperature at which the diamine component and the tetracarboxylic acid derivative are polymerized in an organic solvent is usually from 0 to 150 ° C, preferably from 5 to 100 ° C, preferably from 10 to 80 ° C. The polymerization reaction ends earlier in the higher temperature, but if it is too high, a high molecular weight polymer cannot be obtained. Further, the polymerization reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction liquid is too high and uniform. The stirring becomes difficult, so it is preferably 1 to 50% by mass, preferably 5 to 30% by mass. The initial stage of the polymerization is carried out at a high concentration, and then an organic solvent can be added. Agent. Further, the above-described loading concentration is a concentration in which the total mass of the diamine component and the tetracarboxylic acid derivative is combined.
使用於上述聚合反應時的有機溶劑僅為可溶解所生成之聚醯胺酸及聚醯胺酸酯(以下有時稱為聚醯胺酸(酯))者即可,並無特別限定。作為具體例子,可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯等。這些可單獨亦可混合後使用。且亦可為不溶解聚醯胺酸(酯)之溶劑,在不析出所生成之聚醯胺酸(酯)的範圍下可混合於上述溶劑後使用。 The organic solvent used in the above polymerization reaction is not particularly limited as long as it is a polylysine which can be dissolved and a polyglycolate (hereinafter sometimes referred to as polyglycolic acid). Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and dimethyl group. Azulene, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone and the like. These can be used alone or in combination. Further, it may be a solvent which does not dissolve polyglycolic acid (ester), and may be used after being mixed with the above solvent in the range in which the produced polyglycolic acid (ester) is not precipitated.
又,有機溶劑中之水分會阻礙聚合反應,且造成水解所生成之聚醯胺酸(酯)的原因,故有機溶劑盡量使用經過脫水乾燥者為佳。 Further, since the water in the organic solvent hinders the polymerization reaction and causes the polyamic acid (ester) formed by the hydrolysis, it is preferred that the organic solvent is used as it is after dehydration.
使用於得到聚醯胺酸之聚合反應的四羧酸衍生物與二胺的比率,對莫耳比而言以1:0.8~1:1.2者為佳,該莫耳比越接近1:1時,所得之聚醯胺酸的分子變的越大。聚醯胺酸(酯)的分子量若過小時,所得之塗膜的強度並非充分,相反地若聚醯胺酸(酯)的分子量過大時,所得之液晶配向劑的黏度會過高,塗膜形成時之作業性、塗膜的均勻性等會有惡化的情況。因此,使用於本發明的液晶配向劑之聚醯胺酸(酯)的重量平均分子量以2,000~500,000為佳,較佳為5,000~300,000。 The ratio of the tetracarboxylic acid derivative to the diamine used for obtaining the polymerization reaction of polylysine is preferably from 1:0.8 to 1:1.2 for the molar ratio, and the closer the molar ratio is to 1:1. The larger the molecular weight of the obtained poly-proline. If the molecular weight of the polyglycolic acid (ester) is too small, the strength of the obtained coating film is not sufficient. Conversely, if the molecular weight of the polyamic acid (ester) is too large, the viscosity of the obtained liquid crystal alignment agent is too high, and the coating film is too high. The workability at the time of formation, the uniformity of the coating film, and the like may be deteriorated. Therefore, the polyglycolic acid (ester) used in the liquid crystal alignment agent of the present invention has a weight average molecular weight of preferably 2,000 to 500,000, preferably 5,000 to 300,000.
本發明的液晶配向劑所含有之聚醯胺酸(酯)雖由二 胺成分與四羧酸衍生物之反應而得,作為二胺成分,使用上述式(1)所示特定二胺化合物為必須成分。 The polyphthalic acid (ester) contained in the liquid crystal alignment agent of the present invention is composed of two The reaction of the amine component with the tetracarboxylic acid derivative is carried out, and as the diamine component, the specific diamine compound represented by the above formula (1) is used as an essential component.
又,作為二胺成分,除可使用上述式(1)所示特定二胺化合物以外,亦可使用含有上述式(AM1)所示二胺化合物之二胺成分或可進一步使用含有此以外的二胺化合物之二胺成分。 Further, as the diamine component, in addition to the specific diamine compound represented by the above formula (1), a diamine component containing the diamine compound represented by the above formula (AM1) may be used, or two other components may be further used. a diamine component of an amine compound.
作為四羧酸衍生物,含有上述芳香族四羧酸衍生物之四羧酸衍生物的使用為佳。 As the tetracarboxylic acid derivative, the use of the tetracarboxylic acid derivative containing the above aromatic tetracarboxylic acid derivative is preferred.
所得之聚醯胺酸可由下述式(3)的重複單位所表示。 The obtained polyaminic acid can be represented by a repeating unit of the following formula (3).
又,聚醯胺酸酯可由下述式(4)所表示。 Further, the polyglycolate can be represented by the following formula (4).
上述式(3)、(4)中,Ra、Rb、及Rc為獨立表示來自上述式(1)或上述式(AM1)所示二胺化合物的基。 In the above formulae (3) and (4), R a , R b and R c each independently represent a group derived from the diamine compound represented by the above formula (1) or the above formula (AM1).
使用上述式(1)所示特定二胺化合物,Ra及Rb為氫原子,Rc為-伸苯基-Y1-NH-CX-HN-R2-Y2-伸苯基-。使用上述式(AM1)所示二胺化合物時,Ra為R3,Rb為R4,Rc為R5。 Using the specific diamine compound represented by the above formula (1), R a and R b are a hydrogen atom, and R c is a -phenyl-Y 1 -NH-CX-HN-R 2 -Y 2 -phenylene group. When the diamine compound represented by the above formula (AM1) is used, R a is R 3 , R b is R 4 , and R c is R 5 .
R6與上述式(2-a)~式(2-e)所示四羧酸衍生物中之R6相同意味。 R 6 has the same meaning as R 6 in the tetracarboxylic acid derivative represented by the above formula (2-a) to formula (2-e).
式(4)中之R係來自使用之酯化劑的基。 R in the formula (4) is derived from the group of the esterifying agent used.
如上述所得之聚醯胺酸或聚醯胺酸酯可直接使用於本發明的液晶配向劑。又,於本發明的液晶配向劑,亦可含有將如上述所得之聚醯胺酸或聚醯胺酸酯經脫水閉環的聚醯亞胺者。 The polyamic acid or polyphthalate obtained as described above can be directly used in the liquid crystal alignment agent of the present invention. Further, the liquid crystal alignment agent of the present invention may further contain a polyimine which is subjected to dehydration ring closure of the polylysine or polyglycolate obtained as described above.
本發明的液晶配向劑係為含有如以上所得之聚醯亞胺前驅物者,一般為將彼等聚合物溶解於有機溶劑後成為塗佈液。 The liquid crystal alignment agent of the present invention contains the polyimine precursors obtained as described above, and generally, the polymer is dissolved in an organic solvent to form a coating liquid.
本發明的液晶配向劑除上述聚醯亞胺前驅物以外,亦可含有由該聚醯亞胺前驅物所得之聚醯亞胺、或具有其他結構之聚合物。 The liquid crystal alignment agent of the present invention may contain, in addition to the above polyimide precursor, a polyimine obtained from the polyimide precursor or a polymer having another structure.
本發明的液晶配向劑中之聚醯亞胺前驅物的含有量對於液晶配向劑的全量而言,以1~20質量%為佳,以2~20質量%為較佳。 The content of the polyimine precursor in the liquid crystal alignment agent of the present invention is preferably from 1 to 20% by mass, and preferably from 2 to 20% by mass, based on the total amount of the liquid crystal alignment agent.
本發明的液晶配向劑所含有之有機溶劑僅可溶解所含有之聚合物者即可,並無特別限定。 The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve only the polymer contained therein.
有機溶劑的使用量對於液晶配向劑的全量而言,以80~99質量%為佳,以80~98質量%為較佳。 The amount of the organic solvent used is preferably from 80 to 99% by mass, and preferably from 80 to 98% by mass, based on the total amount of the liquid crystal alignment agent.
作為本發明的液晶配向劑所使用的有機溶劑之具體例,可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N- 甲基-2-吡咯烷酮、N-甲基己內醯胺、2-吡咯烷酮、N-乙基吡咯烷酮、N-乙烯吡咯烷酮、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮等。這些可使用1種或混合2種以上後使用。 Specific examples of the organic solvent used in the liquid crystal alignment agent of the present invention include N,N-dimethylformamide, N,N-dimethylacetamide, and N- Methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, six Methyl hydrazine, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, and the like. These can be used alone or in combination of two or more.
又,即使在單獨不會溶解聚醯亞胺前驅物或聚醯亞胺等的聚合物的溶劑亦可,若為不析出聚合物的範圍,可混合於本發明的液晶配向劑。 Further, the solvent of the polymer such as the polyimine precursor or the polyimide may not be dissolved alone, and may be mixed with the liquid crystal alignment agent of the present invention in the range in which the polymer is not precipitated.
特別為乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸N-丙基酯、乳酸N-丁基酯、乳酸異戊基酯等具有低表面張力之溶劑可藉由混合而提高液晶配向劑對基板的塗膜均勻性。使用這些溶劑時,可使用1種類或混合複數種類使用。 Especially ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- Ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl Ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactic acid A solvent having a low surface tension such as N-propyl ester, N-butyl lactate or isoamyl lactate can improve the uniformity of coating of the liquid crystal alignment agent to the substrate by mixing. When these solvents are used, they can be used in one type or in a mixture of plural types.
對於本發明的液晶配向劑亦以使用具有低表面張力之溶劑為佳,其使用量為液晶配向劑所含之溶劑全體的5~80質量%者為較佳,更佳為20~60質量%。 The liquid crystal alignment agent of the present invention is preferably a solvent having a low surface tension, and the amount thereof is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent. .
本發明的液晶配向劑中除上述聚醯亞胺前驅物、聚醯亞胺等的聚合物、及有機溶劑以外,在不損害本發明的效果範圍內亦可含有各種添加劑。 The liquid crystal alignment agent of the present invention may contain various additives in addition to the above-mentioned polyimine precursor, polymer such as polyimine, and an organic solvent, without impairing the effects of the present invention.
本發明的液晶配向劑中可含有可提高所形成之液晶配 向膜的膜厚均勻性或表面平滑性的添加劑。作為如此添加劑,可舉出氟系界面活性劑、矽氧系界面活性劑、非離子系界面活性劑等。 The liquid crystal alignment agent of the present invention may contain liquid crystal matching which can be formed An additive to the film thickness uniformity or surface smoothness of the film. Examples of such an additive include a fluorine-based surfactant, a rhodium-based surfactant, and a nonionic surfactant.
較具體,例如可舉出EftopEF301、EF303、EF352(Tohken products公司製))、MegafacF171、F173、R-30(大日本ink公司製)、FluoradFC430、FC431(住友3M公司製)、Asahi GuardAG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。這些界面活性劑的使用比率對於液晶配向劑中所含有之聚合物成分的100質量份,較佳0.01~2質量份,更佳為0.01~1質量份。 Specific examples include Eftop EF 301, EF 303, and EF 352 (manufactured by Tohken Products Co., Ltd.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG 710, and Surfon S-. 382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.
本發明的液晶配向劑中可含有提高所形成之液晶配向膜與基板的密著性之添加劑。作為如此添加劑之具體例,可舉出含有官能性矽烷之化合物、含有環氧基之化合物等。 The liquid crystal alignment agent of the present invention may contain an additive which improves the adhesion between the formed liquid crystal alignment film and the substrate. Specific examples of such an additive include a compound containing a functional decane, a compound containing an epoxy group, and the like.
例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲丙基三甲氧基矽烷、3-脲丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基甲矽烷基丙基三伸乙基三胺、N-三甲氧基甲矽烷基丙基三伸乙基三胺、10-三甲氧基甲矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基甲矽烷基-1,4,7-三 氮雜癸烷、9-三甲氧基甲矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基甲矽烷基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(環氧乙烷)-3-胺基丙基三甲氧基矽烷、N-雙(環氧乙烷)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油酯醚、聚乙二醇二縮水甘油酯醚、丙二醇二縮水甘油酯醚、三丙二醇二縮水甘油酯醚、聚丙二醇二縮水甘油酯醚、新戊基甘醇二縮水甘油酯醚、1,6-己二醇二縮水甘油酯醚、甘油二縮水甘油酯醚、2,2-二溴新戊基甘醇二縮水甘油酯醚、1,3,5,6-四縮水甘油酯-2,4-己二醇、N,N,N’,N’,-四縮水甘油酯-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油酯胺基甲基)環己烷、N,N,N’,N’,-四縮水甘油酯-4、4’-二胺基二苯基烷等。 Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltri Ethoxy decane, N-triethoxymethane alkyl propyl triethylamine, N-trimethoxymethyl propyl propyl triethylamine, 10-trimethoxymethyl decyl-1 ,4,7-triazadecane, 10-triethoxymethylidene-1,4,7-three Azadecane, 9-trimethoxycarbamido-3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-Benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane , N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxirane)-3-aminopropyltrimethoxydecane, N-bis(ethylene oxide)-3 -Aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ester ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl ester-m-xylenediamine, 1,3-double (N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylalkane, and the like.
添加這些化合物時,對於液晶配向劑中所含有之聚合物成分的100質量份而言,以0.1~30質量份為佳,較佳為1~20質量份。若未達0.1質量份時,無法期待密著性提高效果,若超過30質量份時,所形成之液晶配向膜的液晶配向性會有降低之情況。 When 100% by mass of the polymer component contained in the liquid crystal alignment agent is added, it is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the adhesion improving effect cannot be expected, and when it exceeds 30 parts by mass, the liquid crystal alignment property of the formed liquid crystal alignment film may be lowered.
本發明的液晶配向劑中,除上述添加劑以外,在不損害本發明的效果範圍內,可添加聚合物以外的聚合物成分、變化液晶配向膜的誘電率或導電性等電氣特性為目的之介電體或者導電物質,進一步可添加可提高作為液晶配向膜時的膜硬度或緻密度為目的之交聯性化合物等。 In addition to the above-mentioned additives, the liquid crystal alignment agent of the present invention can be added to a polymer component other than the polymer, and the electrical properties such as the electric conductivity of the liquid crystal alignment film or the electrical conductivity can be changed without impairing the effects of the present invention. Further, a crosslinkable compound or the like which can improve the film hardness or density when the liquid crystal alignment film is used can be added to the electric material or the conductive material.
本發明的液晶配向劑中之固體成分的濃度可依據目的之液晶配向膜的膜厚做適宜變更。又,形成無缺陷的塗膜,且可得到作為液晶配向膜之適當膜厚,聚合物之濃度以1~20質量%為佳,較佳為2~10質量%。 The concentration of the solid component in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film. Further, a coating film having no defects is formed, and a suitable film thickness as a liquid crystal alignment film can be obtained, and the concentration of the polymer is preferably 1 to 20% by mass, preferably 2 to 10% by mass.
又,對於本發明之液晶配向劑,與上述聚醯亞胺前驅物之同時,可摻合由相異分子結構所成的可溶性聚醯亞胺、聚醯胺酸、聚醯胺酸酯等而使其含有。此時,考慮到所得之聚醯亞胺膜具有所望特性,將上述本發明的聚醯亞胺前驅物之含有量對於合併其他含有之可溶性聚醯亞胺、聚醯胺酸、或聚醯胺酸酯等全量(100莫耳%)而言,以5~95莫耳%者為佳,以10~90莫耳%者為較佳。 Further, the liquid crystal alignment agent of the present invention may be blended with a soluble polyimine, polylysine, polyamine or the like which is formed of a dissimilar molecular structure at the same time as the polyimine precursor. It contains. At this time, in view of the desired properties of the obtained polyimide film, the content of the above-mentioned polyimine precursor of the present invention is combined with other soluble polyimine, polylysine, or polyamine. The total amount (100 mol%) such as an acid ester is preferably from 5 to 95 mol%, more preferably from 10 to 90 mol%.
本發明的液晶配向劑為塗佈於基板上而塗膜,經燒成後,以磨擦處理或光照射等進行配向處理後作為液晶配向膜使用、或在垂直配向用途等上,無經配向處理可作為液晶配向膜使用。 The liquid crystal alignment agent of the present invention is applied to a substrate and coated with a film, and after firing, it is subjected to an alignment treatment by rubbing treatment or light irradiation, and then used as a liquid crystal alignment film or in a vertical alignment application, and is not subjected to alignment treatment. Can be used as a liquid crystal alignment film.
作為所使用之基板,僅為透明性高的基板即可,並無特別限定。例如可使用玻璃基板、丙烯酸基板、聚碳酸酯基板等塑質基板等,使用欲進行液晶驅動的ITO(Indium Tin Oxide)電極等所形成的基板時,由製程簡單化的觀點來看為佳。又,構成反射型液晶顯示元件時,僅於單側基板上亦可使用矽晶圓等不透明物質。作為此時的電極,亦可使用反射鋁等光的材料。 The substrate to be used is only a substrate having high transparency, and is not particularly limited. For example, a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used, and when a substrate formed of an ITO (Indium Tin Oxide) electrode to be liquid-crystal-driven is used, it is preferable from the viewpoint of simplifying the process. Further, when a reflective liquid crystal display device is formed, an opaque substance such as a germanium wafer can be used only on the single-sided substrate. As the electrode at this time, a material that reflects light such as aluminum can also be used.
液晶配向劑之塗佈方法並無特別限定,工業上可使用網版印刷、膠版印刷、柔性版印刷、噴墨印刷等塗佈方 法。作為其他塗佈方法,可使用浸漬、輥塗機、狹縫塗佈機、轉動子等塗佈方法,可配合目的使用。 The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, coating methods such as screen printing, offset printing, flexographic printing, and inkjet printing can be used. law. As another coating method, a coating method such as a dipping, a roll coater, a slit coater, or a rotor can be used, and it can be used for the purpose.
塗佈液晶配向劑之基板的燒成,可在100~350℃的任意溫度下進行,較佳為150~300℃,更佳為180~250℃。 The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of 100 to 350 ° C, preferably 150 to 300 ° C, more preferably 180 to 250 ° C.
於液晶配向劑中含有聚醯胺酸或聚醯胺酸酯時,會依據該燒成溫度而使轉化為聚醯亞胺之轉化率產生變化,但本發明的液晶配向劑無須為100%醯亞胺化。 When the liquid crystal alignment agent contains polyglycolic acid or polyglycolate, the conversion rate of the polyimine is changed depending on the firing temperature, but the liquid crystal alignment agent of the present invention does not need to be 100%. Imine.
且,液晶配向劑之塗膜燒成時間可設定為任意時間。燒成時間若過短時,因殘存溶劑的影響,會有顯示不良產生,較佳為5~60分鐘,更佳為10~40分鐘。 Further, the coating film firing time of the liquid crystal alignment agent can be set to any time. If the firing time is too short, display failure may occur due to the influence of the residual solvent, and it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes.
燒成後之塗膜厚度,若過厚時由液晶顯示元件的消費電力之層面上來看為不利,若過薄時,會有液晶顯示元件之信頼性降低的情況。因此,塗膜厚度較佳為5~300nm,更佳為10~100nm。 When the thickness of the coating film after firing is too thick, it is disadvantageous in terms of the power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, the thickness of the coating film is preferably from 5 to 300 nm, more preferably from 10 to 100 nm.
使液晶呈現水平配向或傾斜配向時,將燒成後的塗膜以磨擦或偏光紫外線照射等進行配向處理為佳。 When the liquid crystal is horizontally aligned or obliquely aligned, it is preferred that the coating film after firing is subjected to alignment treatment by rubbing or polarized ultraviolet rays.
本發明的液晶顯示元件為使用附有電極的基板等,藉由上述手法由本發明的液晶配向劑得到附有液晶配向膜之基板後,以公知方法製作出液晶胞,可作為液晶顯示元件而構成。 In the liquid crystal display device of the present invention, a substrate having an electrode or the like is used, and a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above method, and a liquid crystal cell is produced by a known method, and can be used as a liquid crystal display element. .
對於液晶胞之製作方法,例如可如以下所示。 The method for producing the liquid crystal cell can be, for example, as shown below.
準備於至少一方形成欲使液晶驅動的電極等一對基 板。於該一對基板上,準備形成本發明的液晶配向膜,液晶配向膜所形成之一對基板。其次於單方基板的液晶配向膜上分散間隔物,使液晶配向膜面成為內側下,貼合另一單方的基板,將液晶以減壓注入使其封止。如次製造出液晶顯示元件。 It is prepared to form a pair of bases such as an electrode to be driven by a liquid crystal on at least one of them board. On the pair of substrates, a liquid crystal alignment film of the present invention is prepared, and a liquid crystal alignment film forms a pair of substrates. Next, the spacer is dispersed on the liquid crystal alignment film of the single substrate, the liquid crystal alignment film surface is placed inside, and the other single substrate is bonded, and the liquid crystal is injected under reduced pressure to be sealed. The liquid crystal display element is manufactured as follows.
又,準備本發明的液晶配向膜所形成的一對基板後,於分散間隔物的液晶配向膜面上滴入液晶,其後貼合這些基板後進行封止,製造出液晶顯示元件。且此時的間隔物厚度較佳為1~30μm,更佳為2~10μm。 In addition, after a pair of substrates formed by the liquid crystal alignment film of the present invention are prepared, liquid crystal is dropped onto the liquid crystal alignment film surface of the dispersion spacer, and then these substrates are bonded and sealed to produce a liquid crystal display element. Further, the spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.
如以上,使用本發明的液晶配向劑所製作之本發明的液晶顯示元件為,具有殘像顯像經減低的優良顯示品質的同時,亦具有優良的信頼性之高亮度。因此,在大畫面下的高精細液晶電視、或智慧型手機及平板型裝置等顯示元件上可適當地被利用。 As described above, the liquid crystal display element of the present invention produced by using the liquid crystal alignment agent of the present invention has excellent display quality with reduced afterimage development and high luminance with excellent signalability. Therefore, it can be suitably utilized for a high-definition liquid crystal television in a large screen, or a display element such as a smart phone or a tablet type device.
以下舉出實施例及比較例,藉由本發明做具體說明,但本發明並未僅限定於這些實施例者。 The following examples and comparative examples are specifically described by the present invention, but the present invention is not limited to these examples.
實施例及比較例所使用的簡稱如以下所示。 The abbreviations used in the examples and comparative examples are as follows.
DA-1:1,3-雙(4-胺基苯乙基)脲 DA-1: 1,3-bis(4-aminophenethyl)urea
DA-2:對苯二胺 DA-2: p-phenylenediamine
DA-3:1,5-雙(4-胺基苯氧基)戊烷 DA-3: 1,5-bis(4-aminophenoxy)pentane
DA-4:N-甲基4-胺基苯乙基胺 DA-4: N-methyl 4-aminophenethylamine
DA-5:4,4’-二胺基二苯基烷 DA-5: 4,4'-diaminodiphenylalkane
DA-6:4,4’-二胺基二苯基胺 DA-6: 4,4'-diaminodiphenylamine
DA-7:1,3-雙(4-胺基苯氧基)苯 DA-7: 1,3-bis(4-aminophenoxy)benzene
CA-1:均苯四甲酸二酐 CA-1: pyromellitic dianhydride
CA-2:1,2,3,4-環丁烷四羧酸二酐 CA-2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride
CA-3:5-(2,5-二氧代基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐 CA-3: 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride
CA-4:3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐 CA-4: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride
CA-5:2,5-對苯二甲酸二甲酯基 CA-5: dimethyl 2,5-terephthalate
CA-6:3,3’,4,4’-聯苯基四羧酸二酐 CA-6: 3,3',4,4'-biphenyltetracarboxylic dianhydride
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-1之8.96g(30.0mmol)、及DA-2之3.24g(30.0mmol),加入N-甲基-2-吡咯烷酮141g,一邊運送氮氣一邊進行攪拌並使其溶解。其次一邊攪拌二胺溶液,一邊添加CA-1之12.82g(58.7mmol),進一步添加N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮氣環境下,在水溫下進行20小時攪拌,得到聚醯胺酸(P1)之溶液。將該聚醯胺酸(P1)溶液在25℃下的黏度以E型黏度計(東機產業公司製)做確認時為297mPa.s。 In a 200 ml four-a beaker equipped with a stirring device and a nitrogen inlet tube, 8.96 g (30.0 mmol) of DA-1 and 3.24 g (30.0 mmol) of DA-2 were added, and N-methyl-2-pyrrolidone was added thereto. 141 g was stirred and dissolved while carrying nitrogen gas. Next, while stirring the diamine solution, 12.82 g (58.7 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the temperature was 20 hours at a water temperature in a nitrogen atmosphere. Stirring to obtain a solution of polyamic acid (P1). The viscosity of the polylysine (P1) solution at 25 ° C was 297 mPa when confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). s.
於該聚醯胺酸(P1)溶液50.30g中加入N-甲基-2-吡咯烷酮23.37g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液5.83g、及丁基溶纖劑26.49g, 到P1之濃度為5.5質量%的液晶配向劑。 To 50.30 g of the polyamic acid (P1) solution, 23.37 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. 5.83g, and butyl cellosolve 26.49g, The liquid crystal alignment agent having a concentration of P1 of 5.5% by mass.
表1中表示使用於聚醯胺酸A1之合成的各四羧酸衍生物成分之量(莫耳)與各二胺成分之量(莫耳)。 Table 1 shows the amount (mol) of each tetracarboxylic acid derivative component used in the synthesis of polyamic acid A1 and the amount of each diamine component (mole).
同樣地表1中表示以下實施例2~8及比較例1~6中,於聚醯胺酸(P2~P8及A1~A6)之合成所使用的各四羧酸衍生物成分之量(莫耳)與各二胺成分之量(莫耳)。 Similarly, in Table 1, the amounts of the respective tetracarboxylic acid derivative components used in the synthesis of polyglycine (P2 to P8 and A1 to A6) in the following Examples 2 to 8 and Comparative Examples 1 to 6 are shown. And the amount of each diamine component (mole).
又,表2中表示聚醯胺酸的混合液之A7。 Further, Table 2 shows A7 of a mixed liquid of polylysine.
將所得之液晶配向劑以1.0μm的過濾器過濾後,於附有透明電極之玻璃基板上進行旋轉塗佈,在50℃之加熱板上進行5分鐘乾燥後,在230℃進行30分鐘燒成,得到膜厚70nm之聚醯亞胺膜。該聚醯亞胺膜以嫘縈布磨擦(輥徑120mm、轉動數1000rpm、移動速度30mm/sec、及押入量0.4mm)。將該膜表面使用共焦點雷射顯微鏡(雷射迪克公司製)觀察表面狀態,在倍率10倍下觀察削屑的有無與其尺寸。藉由磨擦之膜削較多時,或具有30μm以上尺寸的膜削產生時,判斷為「不良」。如此現象皆未產生時,判斷耐擦性為「良好」。評估結果如表3所示。 The obtained liquid crystal alignment agent was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 50° C. for 5 minutes, and then fired at 230° C. for 30 minutes. A polyimide film having a film thickness of 70 nm was obtained. The polyimide film was rubbed with a crepe cloth (roll diameter: 120 mm, number of revolutions: 1000 rpm, moving speed: 30 mm/sec, and pushing amount: 0.4 mm). The surface of the film was observed using a confocal laser microscope (manufactured by Laser Dick), and the presence or absence of the shavings and the size thereof were observed at a magnification of 10 times. When the film was cut by a large amount of rubbing or when a film having a size of 30 μm or more was produced, it was judged as "poor". When such a phenomenon has not occurred, it is judged that the rub resistance is "good". The evaluation results are shown in Table 3.
將所得之液晶配向劑以1.0μm過濾器過濾後,於石英基板上進行配向劑之旋轉塗佈塗佈,在50℃的加熱板上進行5分鐘乾燥後,在230℃進行30分燒成,形成膜厚 70nm之聚醯亞胺膜。僅於面向該基板的塗膜面的二邊貼合兩面貼布,與完成未成膜的石英基板進行貼合。於所得之簡易容器中注入流動石蠟,使用島津製作所公司製之UV-3100PC測定透過率。由所得之數據算出視感透過率,其值為96%以上者評估定義為「良好」,未達96%者評估定義為「不良」。評估結果如表3所示。且視感透過率為使用販賣品軟體(島津製作所公司製顏色測量軟體:P/N206-65207)而算出。 The obtained liquid crystal alignment agent was filtered through a 1.0 μm filter, and then spin-coated with an alignment agent on a quartz substrate, dried on a hot plate at 50° C. for 5 minutes, and then fired at 230° C. for 30 minutes. Film thickness 70 nm polyimine film. The two-side patch is bonded only to both sides of the coating film surface facing the substrate, and is bonded to the quartz substrate on which the film is not formed. The liquid paraffin was injected into the obtained simple container, and the transmittance was measured using UV-3100PC manufactured by Shimadzu Corporation. The visual transmittance was calculated from the obtained data. The evaluation value was defined as "good" when the value was 96% or more, and the "bad" was determined when the value was less than 96%. The evaluation results are shown in Table 3. The visual transmittance was calculated using the software for sale (color measurement software manufactured by Shimadzu Corporation: P/N206-65207).
至做出具備IPS(In-Planes Switching)模式液晶顯示元件之構成的液晶胞。 A liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element is prepared.
首先準備附有電極之基板。基板為30mm×50mm的大小,且厚度為0.7mm之玻璃基板。於基板上構成作為第1層的對向電極,形成具備實心狀圖型的ITO電極。於第1層的對向電極上形成作為第2層,且由CVD法所成膜的SiN(氮化矽)膜。第2層的SiN膜之膜厚為500nm,其具有作為層間絶縁膜的功能。於第2層的SiN膜上,製圖且形成作為第3層的ITO膜,配置齒梳狀畫素電極,形成第1畫素及第2畫素之2畫素。各畫素之尺寸為縱10mm且橫約5mm。此時,第1層的對向電極與第3層的畫素電極因藉由第2層的SiN膜作用而成為電絕緣狀態。 First, prepare a substrate with an electrode attached. The substrate was a glass substrate having a size of 30 mm × 50 mm and a thickness of 0.7 mm. A counter electrode as a first layer was formed on the substrate, and an ITO electrode having a solid pattern was formed. A SiN (tantalum nitride) film which is a second layer and is formed by a CVD method is formed on the counter electrode of the first layer. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, an ITO film as a third layer was formed, and a tooth comb-like pixel electrode was placed to form a second pixel of the first pixel and the second pixel. The dimensions of each pixel are 10 mm in length and 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.
第3層的畫素電極為具有配列複數個中央部分彎曲成「ㄑ」字形狀的電極要素所構成之齒梳形狀。各電極要素 之短方向寬為3μm,電極要素間之間隔物為6μm。形成各畫素之畫素電極因係由配列複數的中央部分彎曲成「ㄑ」字形狀的電極要素所構成,故各畫素的形狀並非長方形狀,與電極要素同樣地具備中央部分為彎曲的與粗字體「ㄑ」字相似的形狀。且各畫素係將其中央彎曲部分作為境界進行上下分割,具有彎曲部分的上側第1區域與下側第2區域。 The pixel electrode of the third layer has a tooth comb shape including electrode elements in which a plurality of central portions are bent in a "ㄑ" shape. Electrode element The short direction width was 3 μm, and the spacer between the electrode elements was 6 μm. Since the pixel electrodes forming the respective pixels are composed of electrode elements in which the central portion of the plurality of pixels is bent into a "ㄑ" shape, the shape of each pixel is not rectangular, and the central portion is curved like the electrode elements. A shape similar to the bold font "ㄑ". Each of the pixels has a central curved portion as a boundary and is vertically divided, and has an upper first region and a lower second region having a curved portion.
比較各畫素之第1區域與第2區域時,成為構成這些的畫素電極之電極要素形成方向相異者。即,將後述液晶配向膜的磨擦方向作為基準時,在畫素第1區域中使畫素電極的電極要素呈+10°的角度(順時鐘方向)而形成,在畫素第2區域中使畫素電極的電極要素呈-10°的角度(順時鐘方向)而形成。即,在各畫素的第1區域與第2區域中,藉由畫素電極與對向電極之間的電壓輸入所引起的液晶之在基板面內的轉動動作(面內切換)方向,相互成為逆方向而構成。 When the first region and the second region of each pixel are compared, the electrode elements forming the pixel elements are different in the direction in which they are formed. In other words, when the rubbing direction of the liquid crystal alignment film to be described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of +10° (clockwise direction) in the first region of the pixel, and is formed in the second region of the pixel. The electrode elements of the pixel electrodes are formed at an angle of -10° (clockwise). In other words, in the first region and the second region of each pixel, the direction of the rotation (in-plane switching) of the liquid crystal in the substrate surface caused by the voltage input between the pixel electrode and the counter electrode is mutually It is formed in the reverse direction.
其次,將所得之液晶配向劑以1.0μm的過濾器過濾後,於準備的上述附有電極之基板、與於裏面有ITO膜成膜之玻璃基板上各進行旋轉塗佈。其次在50℃的加熱板上進行5分鐘乾燥後,在230℃進行30分鐘燒成,進行膜厚70nm之塗膜,於各基板上得到聚醯亞胺膜。將該聚醯亞胺膜上在所定磨擦方向,以嫘縈布進行磨擦(輥徑120mm、轉動數500rpm、移動速度30mm/sec、及押入量0.3mm)後,在純水中進行1分鐘超音波照射,並在80℃ 進行10分鐘乾燥。 Next, the obtained liquid crystal alignment agent was filtered through a 1.0 μm filter, and then spin-coated on each of the prepared electrode-attached substrate and the glass substrate on which the ITO film was formed. Subsequently, the film was dried on a hot plate at 50 ° C for 5 minutes, and then fired at 230 ° C for 30 minutes to form a film having a film thickness of 70 nm, and a polyimide film was obtained on each substrate. The polyimide film was rubbed with a crepe in a predetermined rubbing direction (roller diameter: 120 mm, number of revolutions: 500 rpm, moving speed: 30 mm/sec, and amount of impregnation: 0.3 mm), and then carried out in pure water for 1 minute. Sound wave illumination, and at 80 ° C Dry for 10 minutes.
其後,僅於單方基板上,散布4μm之珠子間隔物(日揮觸媒化成公司製)。使用經如此處理的附有液晶配向膜之2種類基板,組合成各磨擦方向呈逆平行,留下液晶注入口而封住周圍,製作出胞間隙為3.6μm之空胞。於該空胞中在常溫下真空注入液晶(MLC-2041、Merck公司製)後,將注入口封止後作為反平行配向之液晶胞。所得之液晶胞構成IPS模式液晶顯示元件。其後,將所得之液晶胞在110℃進行1小時加熱後,放置一晚後使用於各評估。 Thereafter, a 4 μm bead spacer (manufactured by Nikko Kasei Co., Ltd.) was spread only on the single substrate. Two types of substrates with the liquid crystal alignment film thus treated were used, and the rubbing directions were combined to be antiparallel to each other, leaving a liquid crystal injection port to seal the surroundings, and a cell having a cell gap of 3.6 μm was produced. After liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected into the cells at room temperature, the injection port was sealed and used as an antiparallel alignment liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour, and then left for one night and used for each evaluation.
使用以下光學系統等進行殘像評估。 The afterimage evaluation was performed using the following optical system or the like.
將所製作的液晶胞設置於配置成偏光軸為直交的2片偏光板之間,電壓無輸入的狀態下使LED背光點燈,調整液晶胞的配置角度至透過光的亮度為最小。 The produced liquid crystal cell is placed between two polarizing plates arranged such that the polarizing axis is orthogonal, and the LED backlight is turned on while the voltage is not input, and the arrangement angle of the liquid crystal cell is adjusted to minimize the brightness of the transmitted light.
其次,一邊於該液晶胞輸入周波數30Hz的交流電壓,一邊測定V-T曲線(電壓-透過率曲線),算出相對透過率為23%的交流電壓作為驅動電壓。 Next, a V-T curve (voltage-transmittance curve) was measured while inputting an AC voltage having a cycle number of 30 Hz to the liquid crystal cell, and an AC voltage having a relative transmittance of 23% was calculated as a driving voltage.
殘像評估為一邊輸入相對透過率成為23%的周波數30Hz之交流電壓,使液晶胞驅動下,一邊同時輸入2V的直流電壓,使其進行120分鐘驅動。其後,將輸入直流電壓值作為0V,僅停止直流電壓的輸入,在該狀態下進一步進行60分鐘驅動。 The afterimage was evaluated by inputting an AC voltage of 30 Hz with a relative transmittance of 23%, and driving the liquid crystal cell while simultaneously inputting a DC voltage of 2 V to drive for 120 minutes. Thereafter, the input DC voltage value was set to 0 V, and only the input of the DC voltage was stopped, and in this state, the drive was further performed for 60 minutes.
殘像評估為自停止直流電壓的輸入之時間點至經過60 分鐘後,於相對透過率恢復至25%以下時評估為「良好」。相對透過率恢復至25%以下所需時間為60分鐘以上時評估為「不良」。 The afterimage is evaluated as the time from the stop of the input of the DC voltage to 60 After a minute, it was evaluated as "good" when the relative transmittance was restored to 25% or less. The "bad" was evaluated when the time required for the transmittance to return to 25% or less was 60 minutes or longer.
依據上述方法的殘像評估為,在液晶胞之溫度為23℃的狀態與60℃的狀態之2種溫度條件下進行。評估結果如表3所示。 The afterimage evaluation by the above method was carried out under two kinds of temperature conditions of a state in which the temperature of the liquid crystal cell was 23 ° C and a state of 60 ° C. The evaluation results are shown in Table 3.
準備與使用於上述殘像評估的液晶胞的同樣結構之液晶胞。 A liquid crystal cell of the same structure as that used for the liquid crystal cell of the afterimage evaluation described above was prepared.
使用該液晶胞,在60℃的恆溫環境下以周波數30Hz輸入8VPP的交流電壓100小時。其後,將液晶胞之畫素電極與對向電極之間設定為短路狀態,此狀況下在室溫下放置一天。 Using this liquid crystal cell, an AC voltage of 8 V PP was input at a cycle number of 30 Hz for 100 hours in a constant temperature environment of 60 °C. Thereafter, a short circuit state between the pixel electrode of the liquid crystal cell and the counter electrode was set, and in this case, it was left at room temperature for one day.
放置後,將液晶胞設置於配置成偏光軸呈直交的2片偏光板之間,在無電壓輸入的狀態下使背光點燈,調整液晶胞的配置角度至透過光亮度的最小。且自第1畫素的第2區域為最暗之角度至第1區域最暗的角度,算出使液晶胞轉動時的轉動角度作為角度△。對於第2畫素亦同樣地進行,比較第2區域與第1區域,算出同樣角度△。且,將第1畫素與第2畫素之角度△值的平均值作為液晶胞之角度△而算出。該液晶胞之角度△的值若超過0.2度時,評估定義為「不良」。該液晶胞的角度△的值不超過0.2度時,評估為「良好」。評估結果如表3所示。 After being placed, the liquid crystal cell is placed between two polarizing plates arranged so that the polarizing axis is orthogonal, and the backlight is turned on without voltage input, and the arrangement angle of the liquid crystal cells is adjusted to the minimum of the transmitted light brightness. Further, from the darkest angle of the second region of the first pixel to the darkest angle of the first region, the angle of rotation when the liquid crystal cell is rotated is calculated as the angle Δ. Similarly to the second pixel, the second region and the first region are compared, and the same angle Δ is calculated. Further, the average value of the angle Δ values of the first pixel and the second pixel is calculated as the angle Δ of the liquid crystal cell. When the value of the angle Δ of the liquid crystal cell exceeds 0.2 degrees, the evaluation is defined as "poor". When the value of the angle Δ of the liquid crystal cell did not exceed 0.2, it was evaluated as "good". The evaluation results are shown in Table 3.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-1之7.46g(25.0mmol)、及DA-3之7.15g(25.0mmol),加入N-甲基-2-吡咯烷酮143.3g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液下,一邊加入CA-1之10.26g(47.0mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮氣環境下,在水溫下進行20小時攪拌,得到聚醯胺酸(P2)之溶液。將該聚醯胺酸(P2)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到305mPa.s。 In a 200 ml four-beat beaker equipped with a stirring device and a nitrogen inlet tube, 7.46 g (25.0 mmol) of DA-1 and 7.15 g (25.0 mmol) of DA-3 were placed, and N-methyl-2-pyrrolidone was added thereto. 143.3 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 10.26 g (47.0 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass. Under a nitrogen atmosphere, the temperature was 20. After stirring for a while, a solution of polyglycine (P2) was obtained. The viscosity of the polyamic acid (P2) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 305 mPa. s.
於該聚醯胺酸(P2)溶液50.40g中,加入N-甲基-2-吡咯烷酮22.07g、含有3-胺基丙基三乙氧基矽烷1.0質量%的N-甲基-2-吡咯烷酮溶液5.74g、及丁基溶纖劑26.07g,得到P2之濃度為5.5質量%之液晶配向劑。 To 50.40 g of the polyplysine (P2) solution, 22.07 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. 5.74 g of a solution and 26.07 g of butyl cellosolve were used to obtain a liquid crystal alignment agent having a P2 concentration of 5.5% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之4.47 g(15.0mmol)、及DA-2之1.62g(15.0mmol),加入N-甲基-2-吡咯烷酮62.9g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液下,一邊加入CA-3之1.59g(6.0mmol)、及N-甲基-2-吡咯烷酮9.0g,一邊送入氮氣一邊攪拌。經3小時攪拌後,加 入CA-1之5.04g(23.1mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在水溫下攪拌20小時後得到聚醯胺酸(P3)之溶液。將該聚醯胺酸(P3)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到280mPa.s。 Into a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube, 4.47 g (15.0 mmol) of DA-1 and 1.62 g (15.0 mmol) of DA-2 were added, and N-methyl-2-pyrrolidone was added thereto. 62.9 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 1.59 g (6.0 mmol) of CA-3 and 9.0 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred while supplying nitrogen gas. After stirring for 3 hours, add 5.04 g (23.1 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred at a water temperature for 20 hours in a nitrogen atmosphere to obtain a poly-proline (P3). ) a solution. The viscosity of the polyamic acid (P3) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 280 mPa. s.
於該聚醯胺酸(P3)溶液83.48g中加入N-甲基-2-吡咯烷酮26.92g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液9.60g、及丁基溶纖劑40.0g,得到P3之濃度為6.0質量%的液晶配向劑。 To 83.48 g of the polyproline (P3) solution, 26.92 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. 9.60 g and 40.0 g of butyl cellosolve gave a liquid crystal alignment agent having a P3 concentration of 6.0% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之4.83g(16.2mmol)、及DA-2之1.17g(10.8mmol),加入N-甲基-2-吡咯烷酮62.4g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液,一邊加入CA-3之2.85g(10.8mmol)、及N-甲基-2-吡咯烷酮8.9g,一邊送入氮,一邊攪拌。3小時攪拌後加入CA-1之3.30g(15.1mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在水溫進行20小時攪拌後得到聚醯胺酸(P4)之溶液。將該聚醯胺酸(P4)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到288mPa.s。 Into a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube, 4.83 g (16.2 mmol) of DA-1 and 1.17 g (10.8 mmol) of DA-2 were placed, and N-methyl-2-pyrrolidone was added thereto. 62.4 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 2.85 g (10.8 mmol) of CA-3 and 8.9 g of N-methyl-2-pyrrolidone were added, and nitrogen was added thereto while stirring. After stirring for 3 hours, 3.30 g (15.1 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred at a water temperature for 20 hours in a nitrogen atmosphere to obtain a polyfluorene. A solution of the amine acid (P4). The viscosity of the polyamic acid (P4) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 288 mPa. s.
於該聚醯胺酸(P4)溶液82.76g中加入N-甲基-2-吡咯烷酮27.64g、含有3-胺基丙基三乙氧基矽烷1.0質量% 之N-甲基-2-吡咯烷酮溶液9.60g、及丁基溶纖劑40.0g,得到P4之濃度為6.0質量%的液晶配向劑。 To 82.76 g of the polyamic acid (P4) solution, 27.64 g of N-methyl-2-pyrrolidone and 1.0% by mass of 3-aminopropyltriethoxydecane were added. The N-methyl-2-pyrrolidone solution was 9.60 g and the butyl cellosolve 40.0 g, and a liquid crystal alignment agent having a P4 concentration of 6.0% by mass was obtained.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之1.85g(6.2mmol)、及DA-2之1.34g(12.4mmol)及DA-3之3.55g(12.4mmol),加入N-甲基-2-吡咯烷酮64.7g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液,一邊加入CA-2之2.43g(12.4mmol)、及N-甲基-2-吡咯烷酮9.5g,一邊送入氮,一邊攪拌。1小時攪拌後加入CA-1之3.58g(16.4mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在水溫進行20小時攪拌後得到聚醯胺酸(P5)之溶液。將該聚醯胺酸(P5)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到264mPa.s。 1.85 g (6.2 mmol) of DA-1, 1.34 g (12.4 mmol) of DA-2, and 3.55 g (12.4 mmol) of DA-3 were placed in a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube. 64.7 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 2.43 g (12.4 mmol) of CA-2 and 9.5 g of N-methyl-2-pyrrolidone were added, and nitrogen was added while stirring. After stirring for 1 hour, 3.58 g (16.4 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred at a water temperature for 20 hours in a nitrogen atmosphere to obtain a polyfluorene. A solution of aminic acid (P5). The viscosity of the polyamic acid (P5) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 264 mPa. s.
於該聚醯胺酸(P5)溶液84.21g中加入N-甲基-2-吡咯烷酮26.19g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液9.60g、及丁基溶纖劑40.0g,得到P5之濃度為6.0質量%的液晶配向劑。 To 84.21 g of the polyproline (P5) solution, 26.19 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. 9.60 g and 40.0 g of butyl cellosolve gave a liquid crystal alignment agent having a P5 concentration of 6.0% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之4.62g(15.5mmol)、及DA-2之1.68g (15.5mmol),加入N-甲基-2-吡咯烷酮62.9g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液,一邊加入CA-2之1.22g(6.2mmol)、及N-甲基-2-吡咯烷酮8.7g,一邊送入氮,一邊攪拌。1小時攪拌後,加入CA-1之5.04g(23.1mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在水溫進行20小時攪拌後得到聚醯胺酸(P6)之溶液。將該聚醯胺酸(P6)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到262mPa.s。 Into a 100 ml four-beat beaker equipped with a stirring device and a nitrogen introduction tube, 4.62 g (15.5 mmol) of DA-1 and 1.68 g of DA-2 were placed. (15.5 mmol), 62.9 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 1.22 g (6.2 mmol) of CA-2 and 8.7 g of N-methyl-2-pyrrolidone were added, and nitrogen was added while stirring. After stirring for 1 hour, 5.04 g (23.1 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred at a water temperature for 20 hours in a nitrogen atmosphere to obtain a poly A solution of proline (P6). The viscosity of the polyamic acid (P6) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 262 mPa. s.
於該聚醯胺酸(P6)溶液84.96g加入N-甲基-2-吡咯烷酮25.44g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液9.60g、及丁基溶纖劑40.0g,得到P6之濃度為6.0質量%之液晶配向劑。 To the 84.96 g of the polyaminic acid (P6) solution, 25.44 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g, and 40.0 g of butyl cellosolve, a liquid crystal alignment agent having a P6 concentration of 6.0% by mass was obtained.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-1之10.39g(34.8mmol)、及DA-2之2.51g(23.2mmol),加入N-甲基-2-吡咯烷酮142.9g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液,一邊加入CA-2之3.87g(19.7mmol)、及N-甲基-2-吡咯烷酮35.0g,一邊送入氮,一邊攪拌。2小時攪拌後加入CA-1之7.82g(35.9mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在水溫進行20小時攪拌後得到聚醯胺酸(P7)之溶液。將該聚醯 胺酸(P7)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到328mPa.s。 Into a 200 ml four-a beaker equipped with a stirring device and a nitrogen inlet tube, 10.39 g (34.8 mmol) of DA-1 and 2.51 g (23.2 mmol) of DA-2 were added, and N-methyl-2-pyrrolidone was added thereto. 142.9 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 3.87 g (19.7 mmol) of CA-2 and 35.0 g of N-methyl-2-pyrrolidone were added, and nitrogen was added thereto while stirring. After stirring for 2 hours, 7.82 g (35.9 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass. Under a nitrogen atmosphere, the mixture was stirred at a water temperature for 20 hours to obtain a polyfluorene. A solution of aminic acid (P7). The poly The viscosity of the amino acid (P7) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 328 mPa. s.
於該聚醯胺酸(P7)溶液105.08g加入N-甲基-2-吡咯烷酮42.93g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液12.0g、及丁基溶纖劑40.0g,得到P7之濃度為6.0質量%的液晶配向劑。 To the 105.08 g of the polyaminic acid (P7) solution, 42.93 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g and butyl cellosolve 40.0 g, and a liquid crystal alignment agent having a P7 concentration of 6.0% by mass was obtained.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-1之4.18g(14.0mmol)、及DA-4之2.10g(14.0mmol),加入N-甲基-2-吡咯烷酮70.5g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液,一邊加入CA-1之5.86g(26.9mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在水溫進行20小時攪拌後得到聚醯胺酸(P8)之溶液。將該聚醯胺酸(P8)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到311mPa.s。 Into a 200 ml four-a beaker equipped with a stirring device and a nitrogen inlet tube, 4.18 g (14.0 mmol) of DA-1 and 2.10 g (14.0 mmol) of DA-4 were placed, and N-methyl-2-pyrrolidone was added thereto. 70.5 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 5.86 g (26.9 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred at a water temperature for 20 hours in a nitrogen atmosphere. A solution of polyamic acid (P8) is then obtained. The viscosity of the polyamic acid (P8) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 311 mPa. s.
於該聚醯胺酸(P8)溶液55.74g加入N-甲基-2-吡咯烷酮15.61g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液6.2g、及丁基溶纖劑25.85g,得到P8之濃度為6.0質量%的液晶配向劑。 To the 55.74 g of the polyaminic acid (P8) solution, 15.61 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g and butyl cellosolve 25.85 g, and a liquid crystal alignment agent having a P8 concentration of 6.0% by mass was obtained.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中, 放入CA-5之7.94g(28.1mmol)、及N-甲基-2-吡咯烷酮136.5g,經完全溶解。其次加入三乙基胺6.16g、DA-1之4.33g(14.5mmol)、及DA-4之2.18g(14.5mmol),使其完全溶解。其後,將反應液水冷下一邊以磁棒攪拌器進行攪拌,一邊添加二苯基(2,3-二氫-2-硫酮-3-苯並噁唑基)膦酸酯23.35g(60.9mmol),再加入N-甲基-2-吡咯烷酮18.75g,繼續進行5小時攪拌。其後,於攪拌反應溶液之6倍質量的異丙基醇時,徐徐地注入反應溶液並繼續攪拌1小時。其後將經過濾所得之析出物與2倍質量之異丙基醇同時進行1小時攪拌後,再度過濾後回收析出物。其後將該作業進行2次重複,將所得之析出物在100℃、減壓下進行24小時乾燥,得到10.54g之聚醯胺酸酯(P9)。將所得之固形物中5.14g,完全溶解於N-甲基-2-吡咯烷酮37.69g。其次於該溶液中加入N-甲基-2-吡咯烷酮38.55g、及丁基溶纖劑20.10g後得到P9之濃度為4.5質量%的液晶配向劑。 In a 200ml four-beat beaker with a stirring device and a nitrogen inlet tube, 7.94 g (28.1 mmol) of CA-5 and 136.5 g of N-methyl-2-pyrrolidone were placed and completely dissolved. Next, 6.16 g of triethylamine, 4.33 g (14.5 mmol) of DA-1, and 2.18 g (14.5 mmol) of DA-4 were added to completely dissolve. Thereafter, the reaction liquid was stirred with a magnetic stirrer while stirring, and 23.35 g of diphenyl(2,3-dihydro-2-thione-3-benzoxazolyl)phosphonate was added (60.9). Additional), 18.75 g of N-methyl-2-pyrrolidone was added and stirring was continued for 5 hours. Thereafter, while stirring 6 times by mass of the isopropyl alcohol of the reaction solution, the reaction solution was slowly poured and stirring was continued for 1 hour. Thereafter, the precipitate obtained by filtration was stirred with 2 times by mass of isopropyl alcohol for 1 hour, and then filtered again to recover the precipitate. Thereafter, the work was repeated twice, and the obtained precipitate was dried at 100 ° C under reduced pressure for 24 hours to obtain 10.54 g of a polyamine (P9). 5.14 g of the obtained solid matter was completely dissolved in 37.69 g of N-methyl-2-pyrrolidone. Next, 38.55 g of N-methyl-2-pyrrolidone and 20.10 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment agent having a P9 concentration of 4.5% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之1.50g(5.03mmol)、及DA-7之5.85g(20.0mmol),加入N-甲基-2-吡咯烷酮73g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液下,一邊添加CA-1之5.23g(24.0mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮氣環境 下,在水溫下進行20小時攪拌,得到聚醯胺酸(P10)之溶液。將該聚醯胺酸溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到327mPa.s。 Into a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube, 1.50 g (5.03 mmol) of DA-1 and 5.85 g (20.0 mmol) of DA-7 were placed, and N-methyl-2-pyrrolidone was added thereto. 73 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 5.23 g (24.0 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass in a nitrogen atmosphere. The mixture was stirred at a water temperature for 20 hours to obtain a solution of polyglycine (P10). The viscosity of the polyamic acid solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 327 mPa. s.
於該聚醯胺酸溶液35.10g加入N-甲基-2-吡咯烷酮15.49g、及丁基溶纖劑16.86g後,得到P10之濃度為6.0質量%的液晶配向劑。 After adding 15.49 g of N-methyl-2-pyrrolidone and 16.86 g of butyl cellosolve to 35.10 g of the polyamic acid solution, a liquid crystal alignment agent having a P10 concentration of 6.0% by mass was obtained.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之3.73g(12.5mmol)、及DA-7之3.65g(12.5mmol),加入N-甲基-2-吡咯烷酮73g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液下,一邊添加CA-1之5.18g(23.8mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮氣環境下,在水溫下進行20小時攪拌,得到聚醯胺酸(P11)之溶液。將該聚醯胺酸溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到289mPa.s。 Into a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube, 3.73 g (12.5 mmol) of DA-1 and 3.65 g (12.5 mmol) of DA-7 were placed, and N-methyl-2-pyrrolidone was added thereto. 73 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 5.18 g (23.8 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass. Under a nitrogen atmosphere, 20 at a water temperature. After stirring for a while, a solution of polyamic acid (P11) was obtained. The viscosity of the polyamic acid solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 289 mPa. s.
於該聚醯胺酸溶液11.92g中加入N-甲基-2-吡咯烷酮10.74g、及丁基溶纖劑8.00g,得到P11之濃度為4.5質量%的液晶配向劑。 To 11.92 g of the polyamic acid solution, 10.74 g of N-methyl-2-pyrrolidone and 8.00 g of butyl cellosolve were added to obtain a liquid crystal alignment agent having a P11 concentration of 4.5% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之2.21g(7.41mmol)、及DA-7之5.01g (17.1mmol),加入N-甲基-2-吡咯烷酮73g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液下,一邊添加CA-1之5.07g(23.2mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮氣環境下,在水溫下進行20小時攪拌,得到聚醯胺酸(P12)之溶液。將該聚醯胺酸溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到267mPa.s。 2. In a 100 ml four-beat beaker equipped with a stirring device and a nitrogen introduction tube, 2.21 g (7.41 mmol) of DA-1 and 5.01 g of DA-7 were placed. (17.1 mmol), 73 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 5.07 g (23.2 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass. Under a nitrogen atmosphere, the temperature was 20. After stirring for a while, a solution of polyglycine (P12) was obtained. The viscosity of the polyamic acid solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 267 mPa. s.
於該聚醯胺酸溶液49.84g中加入N-甲基-2-吡咯烷酮20.62g、及丁基溶纖劑23.49g,得到P12之濃度為6.0質量%之液晶配向劑。 To 49.84 g of the polyamic acid solution, 20.62 g of N-methyl-2-pyrrolidone and 23.49 g of butyl cellosolve were added to obtain a liquid crystal alignment agent having a P12 concentration of 6.0% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之1.43 g(4.80mmol)、及DA-7之5.61g(19.2mmol),加入N-甲基-2-吡咯烷酮79g,一邊運送氮氣一邊進行攪拌並使其溶解。一邊攪拌該二胺溶液下,一邊添加CA-6之6.77g(23.0mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮氣環境下,在水溫下進行20小時攪拌,得到聚醯胺酸(P13)之溶液。將該聚醯胺酸溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到240mPa.s。 Into a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube, 1.43 g (4.80 mmol) of DA-1 and 5.61 g (19.2 mmol) of DA-7 were placed, and N-methyl-2-pyrrolidone was added thereto. 79 g was stirred and dissolved while carrying nitrogen gas. While stirring the diamine solution, 6.77 g (23.0 mmol) of CA-6 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass. Under a nitrogen atmosphere, the temperature was 20. After stirring for a while, a solution of polyglycine (P13) was obtained. The viscosity of the polyamic acid solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 240 mPa. s.
於該聚醯胺酸溶液14.76g加入N-甲基-2-吡咯烷酮7.22g、及丁基溶纖劑7.32g,得到P13之濃度為6.0質量%的液晶配向劑。 To the 14.76 g of the polyaminic acid solution, 7.22 g of N-methyl-2-pyrrolidone and 7.32 g of butyl cellosolve were added to obtain a liquid crystal alignment agent having a P13 concentration of 6.0% by mass.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-3之17.75g(62.0mmol),加入N-甲基-2-吡咯烷酮139.1g,一邊運送氮氣一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌一邊加入CA-1之12.91g(59.2mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下,在50度下一邊加熱一邊進行20小時攪拌後得到聚醯胺酸(A1)之溶液。將該聚醯胺酸(A1)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到530mPa.s。 17.75 g (62.0 mmol) of DA-3 was placed in a 200 ml four-aluminum beaker equipped with a stirring device and a nitrogen gas introduction tube, and 139.1 g of N-methyl-2-pyrrolidone was added thereto, and the mixture was stirred while carrying nitrogen gas. Dissolved. 12.91 g (59.2 mmol) of CA-1 was added to the diamine solution while stirring under water cooling, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and under a nitrogen atmosphere at 50 degrees. After heating for 20 hours while heating, a solution of polyamic acid (A1) was obtained. The viscosity of the polyamic acid (A1) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 530 mPa. s.
於該聚醯胺酸(A1)溶液50.00g加入N-甲基-2-吡咯烷酮43.95g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液5.6g、及丁基溶纖劑24.89g,得到A1之濃度為4.5質量%的液晶配向劑。 To the 50.00 g of the polyaminic acid (A1) solution, 43.95 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g. and 24.89 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A1 of 4.5% by mass.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-2之3.25g(30.0mmol)、及DA-3之8.60g(30.0mmol),加入N-甲基-2-吡咯烷酮138.1g,一邊運送氮氣一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌一邊加入CA-1之12.59g(57.7mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下進行20小時攪拌後得到聚醯胺酸(A2)之溶 液。將該聚醯胺酸(A2)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到310mPa.s。 Into a 200 ml four-beat beaker equipped with a stirring device and a nitrogen inlet tube, 3.25 g (30.0 mmol) of DA-2 and 8.60 g (30.0 mmol) of DA-3 were placed, and N-methyl-2-pyrrolidone was added thereto. 138.1 g was stirred and dissolved while carrying nitrogen gas. 12.59 g (57.7 mmol) of CA-1 was added to the diamine solution while stirring under water cooling, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred for 20 hours in a nitrogen atmosphere. Getting polylysine (A2) dissolved liquid. The viscosity of the polyamic acid (A2) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 310 mPa. s.
於該聚醯胺酸(A2)溶液52.34g加入N-甲基-2-吡咯烷酮23.18g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液5.98g、及丁基溶纖劑27.17g,得到A2之濃度為5.5質量%之液晶配向劑。 To the 52.34 g of the polyaminic acid (A2) solution, 23.18 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g. and 27.17 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A2 of 5.5% by mass.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-1之7.64g(25.6mmol)、及DA-2之4.15g(38.4mmol),加入N-甲基-2-吡咯烷酮141.6g,一邊運送氮氣一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌一邊加入CA-2之6.81g(34.7mmol)及N-甲基-2-吡咯烷酮35.4g,一邊送入氮,一邊攪拌。2小時攪拌後,加入CA-1之5.58g(25.6mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下進行20小時攪拌後得到聚醯胺酸(A3)之溶液。將該聚醯胺酸(A3)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到276mPa.s。 7.4 g (25.6 mmol) of DA-1 and 4.15 g (38.4 mmol) of DA-2 were placed in a 200 ml four-beat beaker equipped with a stirring device and a nitrogen introduction tube, and N-methyl-2-pyrrolidone was added thereto. 141.6 g was stirred and dissolved while carrying nitrogen gas. The diamine solution was added with 6.81 g (34.7 mmol) of CA-2 and 35.4 g of N-methyl-2-pyrrolidone while stirring under water cooling, and the mixture was stirred while feeding nitrogen. After stirring for 2 hours, 5.58 g (25.6 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred for 20 hours in a nitrogen atmosphere to obtain polylysine ( A3) solution. The viscosity of the polyamic acid (A3) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 276 mPa. s.
於該聚醯胺酸(A3)溶液53.33g加入N-甲基-2-吡咯烷酮22.01g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液6.12g、及丁基溶纖劑20.35g,得到A3之濃度為6.0質量%的液晶配向劑。 To the 53.33 g of the polyaminic acid (A3) solution, 22.01 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were dissolved in a solution of 6.12 g. g and butyl cellosolve 20.35 g, and a liquid crystal alignment agent having a concentration of A3 of 6.0% by mass was obtained.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之3.14g(10.5mmol)、及DA-2之2.64g(24.4mmol),加入N-甲基-2-吡咯烷酮71.6g,一邊運送氮氣一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌一邊加入CA-2之6.55g(33.4mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下進行20小時攪拌後得到聚醯胺酸(A4)之溶液。將該聚醯胺酸(A4)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到274mPa.s。 Into a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube, 3.14 g (10.5 mmol) of DA-1 and 2.64 g (24.4 mmol) of DA-2 were placed, and N-methyl-2-pyrrolidone was added thereto. 71.6 g was stirred and dissolved while carrying nitrogen gas. After the diamine solution was stirred under water cooling, 6.55 g (33.4 mmol) of CA-2 was added thereto, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred for 20 hours in a nitrogen atmosphere. A solution of polyamic acid (A4) was obtained. The viscosity of the polyamic acid (A4) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 274 mPa. s.
於該聚醯胺酸(A4)溶液20.09g加入N-甲基-2-吡咯烷酮8.64g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液2.32g、及丁基溶纖劑7.76g,得到A4之濃度為6.0質量%的液晶配向劑。 To the 20.09 g of the polyaminic acid (A4) solution, 8.64 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g and 4.7 cellosolve of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A4 of 6.0% by mass.
於附有攪拌裝置及氮導入管之100ml四口燒杯中,放入DA-1之0.84g(28mmol)、及DA-2之1.21g(11.2mmol)、DA-3之4.01g(14.0mmol),加入N-甲基-2-吡咯烷酮72.6g,一邊運送氮氣一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌一邊加入CA-3之2.67g(10.1mmol)。經2小時攪拌後加入CA-1之3.66g(16.8mmol),進一步加入N-甲基-2-吡咯烷酮至固體成分濃度成為12質量%,氮環境下進行20小時攪拌後得到 聚醯胺酸(A5)之溶液。將該聚醯胺酸(A5)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到358mPa.s。 0.81 g (28 mmol) of DA-1, 1.21 g (11.2 mmol) of DA-2, and 4.01 g (14.0 mmol) of DA-3 were placed in a 100 ml four-a beaker equipped with a stirring device and a nitrogen introduction tube. Then, 72.6 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while carrying nitrogen gas. 2.67 g (10.1 mmol) of CA-3 was added to the diamine solution while stirring under water cooling. After stirring for 2 hours, 3.66 g (16.8 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added until the solid content concentration became 12% by mass, and the mixture was stirred for 20 hours in a nitrogen atmosphere. A solution of polyamic acid (A5). The viscosity of the polyamic acid (A5) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 358 mPa. s.
於該聚醯胺酸(A5)溶液50.59g加入N-甲基-2-吡咯烷酮14.51g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液5.66g、及丁基溶纖劑23.59g,得到A5之濃度為6.0質量%的液晶配向劑。 To the 50.59 g of the polyaminic acid (A5) solution, 14.51 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g. and 23.59 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A5 of 6.0% by mass.
於附有攪拌裝置及氮氣導入管的200ml四口燒杯中,放入DA-6之7.97g(40.0mmol),N-甲基-2-吡咯烷酮98.6g,一邊運送氮氣一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌一邊加入CA-2之6.96g(35.5mmol)與N-甲基-2-吡咯烷酮35.9g,氮環境下,水冷下進行3小時攪拌。其後加入DA-5之1.98g(10.0mmol)與N-甲基-2-吡咯烷酮17.9g,進行攪拌使其溶解。DA-5經溶解後加入CA-4之3.00g(10.0mmol)與N-甲基-2-吡咯烷酮26.9g,再次在氮環境下,水冷下進行3小時攪拌後得到聚醯胺酸(A6)之溶液。將該聚醯胺酸(A6)溶液的25℃中之黏度以E型黏度計(東機產業公司製)確認後得到165mPa.s。 7.97 g (40.0 mmol) of DA-6 and 98.6 g of N-methyl-2-pyrrolidone were placed in a 200 ml four-aluminum beaker equipped with a stirring device and a nitrogen introduction tube, and the mixture was stirred and dissolved while carrying nitrogen gas. . To the diamine solution, 6.96 g (35.5 mmol) of CA-2 and 35.9 g of N-methyl-2-pyrrolidone were added while stirring under water cooling, and the mixture was stirred under water cooling for 3 hours under nitrogen atmosphere. Thereafter, 1.98 g (10.0 mmol) of DA-5 and 17.9 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred and dissolved. After dissolving DA-5, 3.00 g (10.0 mmol) of CA-4 and 26.9 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred under nitrogen for 3 hours under water to obtain polylysine (A6). Solution. The viscosity of the polyamic acid (A6) solution at 25 ° C was confirmed by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.) to obtain 165 mPa. s.
於該聚醯胺酸(A6)溶液50.00g加入N-甲基-2-吡咯烷酮10.55g、含有3-胺基丙基三乙氧基矽烷1.0質量%之N-甲基-2-吡咯烷酮溶液4.9g、及丁基溶纖劑16.37g,得 到A6之濃度為6.0質量%的溶液。 To the 50.00 g of the polyaminic acid (A6) solution, 10.55 g of N-methyl-2-pyrrolidone and 1.0% by mass of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. g, and butyl cellosolve 16.37g, A solution having a concentration of 6.0% by mass to A6.
又,於A1的聚醯胺酸溶液50.00g中加入N-甲基-2-吡咯烷酮24.67g及丁基溶纖劑18.66g,得到A1之濃度為6.0質量%的液晶配向劑。將該二種6.0質量%之溶液以A1:A6為2:8的分量進行混合後得到聚醯胺酸溶液A7。 Further, 24.67 g of N-methyl-2-pyrrolidone and 18.66 g of butyl cellosolve were added to 50.00 g of a polyamine acid solution of A1 to obtain a liquid crystal alignment agent having a concentration of A1 of 6.0% by mass. The two 6.0% by mass solutions were mixed in a ratio of A1:A6 of 2:8 to obtain a polyamic acid solution A7.
使用實施例2~13、及比較例1~6所得之液晶配向劑,與實施例1同樣下,製作出膜或液晶胞等評估試料,進行耐擦性、視感透過率評估、殘像評估、及長期驅動引起的殘像評估。所得之結果如表3所示。 Using the liquid crystal alignment agents obtained in Examples 2 to 13 and Comparative Examples 1 to 6, an evaluation sample such as a film or a liquid crystal cell was prepared in the same manner as in Example 1, and scratch resistance, visual transmittance evaluation, and afterimage evaluation were performed. And afterimage evaluation caused by long-term driving. The results obtained are shown in Table 3.
使用實施例1~13之液晶配向劑所形成之膜中,其耐擦性為良好,且透過率亦為良好。且,作為液晶胞的評估中之液晶配向膜適用時,並無殘像評估之溫度依賴性,長期驅動引起的殘像評估結果亦為良好。 In the film formed using the liquid crystal alignment agents of Examples 1 to 13, the rubbing resistance was good and the transmittance was also good. Further, when it is applied to the liquid crystal alignment film in the evaluation of the liquid crystal cell, there is no temperature dependence of the afterimage evaluation, and the afterimage evaluation result by long-term driving is also good.
另一方面,使用比較例1~6的液晶配向劑所形成之液晶配向膜中,其為難兼備殘像特性與高透過率、以及耐擦性,得知無法使所有項目皆為良好。作為二胺成分未使用DA-1的比較例1及比較例2、以及作為二胺成分之DA-1的使用量較少的比較例5中,得知其耐擦性不良。 On the other hand, in the liquid crystal alignment film formed using the liquid crystal alignment agents of Comparative Examples 1 to 6, it was difficult to provide both afterimage characteristics, high transmittance, and rub resistance, and it was found that all the items could not be made good. Comparative Example 1 and Comparative Example 2 in which DA-1 was not used as the diamine component, and Comparative Example 5 in which DA-1 was used as the diamine component was found to have poor rubbing resistance.
於四羧酸衍生物成分未使用CA-1的比較例4及導入量較少的比較例3中,在23℃之殘像回復為不良,有關比較例4得知長期驅動引起的殘像評估之結果亦為不良。 In Comparative Example 4 in which the tetracarboxylic acid derivative component was not used for CA-1 and Comparative Example 3 in which the amount of introduction was small, the afterimage at 23 ° C was returned to be poor, and Comparative Example 4 was found to be responsible for evaluation of afterimage caused by long-term driving. The result is also bad.
又,未使用DA-1之比較例6中,得知並未得到高視感透過率。 Further, in Comparative Example 6 in which DA-1 was not used, it was found that high visual transmittance was not obtained.
藉由使用本發明的液晶配向劑,可得到具有高透過率,優良耐擦性,殘像等顯示不良在廣溫度範圍下可經改善的液晶配向膜。該液晶配向膜可利用於自過去要求高顯示品質的大型液晶電視上,或近年來急速要求顯示品質提高的行動電話或平板型裝置用液晶顯示元件上。 By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film which has high transmittance, excellent rub resistance, and display defects such as afterimages which can be improved over a wide temperature range can be obtained. The liquid crystal alignment film can be used for a large-sized liquid crystal television that has been required to have high display quality in the past, or a liquid crystal display device for a mobile phone or a flat type device that has been rapidly required to have improved display quality in recent years.
且,2011年10月27日申請的日本專利申請案第2011-235976號的說明書、申請專利範圍、及摘要的全內容皆引用於此,作為本發明之說明書的開示內容。 The entire contents of the specification, the scope of the application, and the abstract of Japanese Patent Application No. 2011-235976, filed on Jan. 27, 2011, are hereby incorporated by reference.
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